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One of the appeals of Unreal Tournament: Game of the Year Edition is the wide variety of weaponry it provides. Unfortunately, with such a variety available, choosing the right gun for a given situation can be difficult, so I've prepared this description of each gun, and its ideal usage. Each one is listed by number, which refers to its location at the bottom of the HUD.

Primary fire is the function accessed by the trigger (usually the left mouse button). Alternate fire is accessed by the secondary trigger (usually the right mouse button).

Translocator

Slot: 1
Description: This "weapon" is used for teleporting from place to place. Simply use alternate fire to shoot the translocator, then use primary fire to teleport to the translocator's new location.
Usage: While it is possible to kill someone by firing the translocator at them, then teleporting on top of them (aka "telefragging"), it's extremely difficult to do and not very reliable. Only use this as a weapon as an absolute last resort (but it makes a great tool!)
Primary Function: Teleport (after firing with secondary)
Secondary Function: Fire Translocator/Remove Fired Translocator

Airhammer

Slot: 1
Description: This is basically a cylinder with a pneumatic ram behind it. Highly lethal, but strictly a melee weapon.
Usage: It's a melee weapon, pretty self-explanatory. It does an acceptable job.
Primary Function: Rapid-fire
Secondary Function: Charge (release to fire, greater damage)

Enforcer

Slot: 2
Description: A simple pistol, the Enforcer is standard issue for all UT games (unless you're using some weird mutator).
Usage: This is a pretty basic weapon, and rather weak, but versatile. If your aim is good enough, the Enforcer can do some serious damage, especially if you have two of them (loot as many as you can from your dead teammates!)
Primary Function: Standard Fire (slower, more accurate)
Secondary Function: Sidearm Stance (faster, less accurate)

Biosludge Rifle

Slot: 3
Description: Usually referred to as the "poop gun", the Biosludge fires the excrement of some exotic fantasy creature that happens to be highly volatile.
Usage: The Biosludge's fired ammo is closely akin to land mines, so fire it into a high-traffic area for fun results. Don't waste your ammo though, the globs explode on their own after a few seconds.
Primary Function: Rapid Fire
Secondary Function: Charge (click & hold to build up a huge glob)

Shock Rifle

Slot: 4
Description: This is one of the best low-end weapons in the game. Simple, accurate, and versatile, the Shock Rifle is an excellent weapon for close and long-range combat.
Usage: The primary function of this gun is instant-hit (despite its delayed-hit animation), and makes a good (though low-power) sniper rifle. The secondary function isn't overly useful, but is well suited for close combat. However, shooting the shock balls with a shock blast will generate a massive explosion. This is tricky to use, but once you learn it, this technique can cause massive amounts of damage, especially in close combat situations.
Primary Function: Insta-Hit Shock Blasts
Secondary Function: Shock Balls

Pulse Cannon

Slot: 5
Description: Another good mid-range weapon, the pulse cannon is a greener, less common cousin of the Shock Rifle
Usage: The Pulse Cannon is, unfortunately, one of the most frequently mis-used weapons in the game. Its primary function (pulse balls) is often overlooked, but is very effective at close range. Its secondary function (and most famous) is a steady green beam that eats through whatever you're aiming at. While fun and unique to use, this beam is actually fairly useless. It has a short range, and fires slower than the primary function, and at point-blank range (where most people try to use it as a last resort), it takes twice as long to make the kill as the primary function. So, save the pretty green beam for targets that are within 20 feet of you, but not closer than 3 feet, and only when aimed at the head. Use the primary function for everything else, or a different gun (something more suited to long-distance shots, perhaps).
Primary Function: Pulse Balls (fire faster than secondary, travel faster than the Shock Rifle's shock balls)
Secondary Function: Pulse Beam (slower, but good when targetted at the head)

Ripper

Slot: 6
Description: One of the most useless guns in the game, the Ripper fires circular razor blades. The bots love this gun.
Usage: The Ripper is usually hated by most UT players and considered to be a waste of a slot, but it does have its niche. This is the only gun that can make more than one ricochet (in a realistic map), and one of two guns that can make a true headshot. So, use this for small indoor spaces where there are lots of enemy targets, and play off the ricochet! It does that for a reason, and you can get 5-6 good ricochets from one shot. Hallways are an excellent place to use this. Don't bother with the secondary function on this gun, only the bots use it, and you're more likely to get a kill with the Translocator than with the Ripper's secondary fire.
Primary Function: Razor Discs
Secondary Function: Exploding Razor Discs (slower, no ricochet, no headshot)

Minigun

Slot: 7
Description: Fast-firing machine gun, uses the same ammo as the Enforcer.
Usage: This gun is pretty over-used, especially by bots. Its primary function is decent enough, but nothing special. Its secondary function is rather poor. Use another gun when possible.
Primary Function: Standard Fire (more accurate)
Secondary Function: Rapid Fire (horribly inaccurate, even at close range, waste of ammo)

Flak Cannon

Slot: 8
Description: My personal favourite, a gun that shoots white-hot shrapnel at your target, much like a shotgun
Usage: This is probably the single-best close range weapon in the game. Two shots with primary fire will kill almost anyone regardless of shielding or armour, and one shot of secondary fire is almost a guaranteed one-hit kill (though the secondary function is harder to hit someone with than primary). It can be used at long-range, but it's not recommended. Also, the primary fire from this gun will ricochet at least once per shot.
Primary Function: Flak Blast (Faster, somewhat less accurate, but more potential per shot in close groups)
Secondary Function: Flak Grenade (No spread, one hit kill, unpredictable flight path)

Rocket Launcher

Slot: 9
Description: A basic rocket launcher, every FPS has one
Usage: UT's rocket launcher isn't very good at its job, it takes 2-3 hits to kill someone even if they have no armour and have already been hit by something. Its secondary fire, grenades, are somewhat better, but still disappointingly weak. It does, however, have something over other games: Multi-Fire. Holding down either firing button will load up to six projectiles in the launcher, and will fire them when the firing button is released, or when six projectiles have been loaded. This is quite useful for close groups, and perfect for the grenades, but it takes awhile to load up multiples, so don't rely on this in a close combat emergency. Also, hovering on a target for a few seconds will lock onto that person, delivering a rocket right to their backside.
Primary Function: Rockets (click & hold to charge multiple shots, hover on target for guided mode)
Secondary Function: Grenades (click & hold to charge multiple shots)

Sniper Rifle

Slot: 10
Description: Generic sniper rifle, nothing unusual here
Usage: Another favourite of mine (that my LAN party mates know very well), the sniper rifle is an amazing all-around weapon. While it's intended for long-range use with the scope, it also works well at medium and close range without it.
Primary Function: Semi-Auto Rifle Shots
Secondary Function: Scope (click & hold to zoom, click again to reset)

Redeemer

Slot: 10
Description: A small nuclear warhead :-D
Usage: This is a very rare weapon, but most maps have one. Its primary fire is rather silly, but its secondary fire (fly-by-wire) is amazing. When using it, steer using the mouse and aim for clusters. The Redeemer's missile can be shot down, though, so fly erratically and make yourself hard to hit. Also, to throw people off and detonate prematurely (in mid-air right in front of a group while they line up shots on you), hit primary fire while flying. The guided flight mode is a bit tricking, I recommend playing single-player and using the cheat codes to practice flying the redeemer when you're not playing multiplayer.
Primary Function: Standard Rocket (flies in a perfectly straight line)
Secondary Function: Fly-By-Wire

Chainsaw (Special)

Slot: 1
Description: Chainsaw massacre, anyone?
Usage: This is only present when using a mutator or cheat code, but it is a force to be reckoned with! This melee weapon is a one-hit kill, and all you have to do to kill someone with it is hit them for about one second with it.
Primary Function: Ordinary Melee (holds one position)
Secondary Function: Slashing Movement (slice your target in half!)

Enhanced Shock Rifle (Special)

Slot: 4
Description: A one-shot-kill version of the Shock Rifle
Usage: This is only present when using the Insta-Gib mutator. You get unlimited ammo, and both triggers do the exact same thing. Excellent practice for no-scope headshots with the sniper rifle. Also, like its less-exciting brother (regular Shock Rifle), the Enhanced Shock Rifle is insta-hit (despite its delayed-hit animation).
Primary Function: One-Shot-Kill Insta-Hit Shock Blast
Secondary Function: One-Shot-Kill Insta-Hit Shock Blast