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So I've got at least 10 missile launchers from my BaC kits and picked up 10x Volkite Culverins cheap on eBay. Is it worth picking up 10x of each of the other heavy weapons so I have them available? Are some just not worth taking or do they all have a use? I'm running Imperial Fists if that makes any difference. I just love the look of marines toting around huge pieces of heavy weaponry.

I would say plasma cannons aren't really worth it. Expensive, you'll fry at least one of your own guys from Gets Hot, and generally waste time scattering ten blasts.
Multimeltas are too short of a range, and because of the possibility of ceramite, are best used against rear armor which really just isn't going to happen.
Lascannons are just freakishly expensive.

Missile launchers are good and fairly cheap. Good range and nice options to do blasts or to crack armor.

As Imp fists (which I am also doing) I took 10 heavy bolter, as a BS of 5 with them is great and they are free to take.

Meltas I think are better on contemptors as they can live usually to get to the target.

I have not taken plasma cannons or lascannons. I did buy 10 auto cannons but dunno when ill ever use them

If you got ten autocannons obviously the answer to the question of when to use them is "every opportunity you have". You get to figure out what they're good for and make every tyranid player within a ten mile radius break out into inexplicable cold sweats.

Missile launchers are nice, but the preponderance of hardened armour on most footslogging marines makes frag missiles kibd of guff.

Massed krak missiles can make a nice mess, though, even if they can't touch the front of a flare shielded tank.

You have tank hunter as standard for heavy weapon squads, take ML, autocannon and lascannon any time you can and volkite is great.

I'm a fan of the missile launcher for my Imperial Fists. The Lascannon does well, but they're expensive and I haven't taken them, much. Lascannons do help against AV14 tanks with Armored Ceremite when you have Tank Hunters!

While I like Autocannons, the Black Book fluff on the Imperial Fists (THE HORUS HERESY BOOK THREE - EXTERMINATION) states that Imperial Fists don't take autocannons so I don't include them. With Tank hunters, they're excellent at popping rhinos when you have a unit of 6 or 7. That's a shame.

Autocannon is where its at if you wanna kill light to medium armour, glancing on a 6 isnt so bad when you are rerolling all fails.