Has anyone been able to successfully pull off one of the "special" moves in VATS using a melee or unarmed weapon?

If you have, please post your Melee Weapons skill and what weapon you used to pull it off!

I have yet to see the option. :/

Also, does anyone know what mods are available for melee weapons? I am making a melee build and was hoping I'd get to make some interesting mods to my weapons

According to JES there are no mods for Melee.

Are there any weapon poisons or anything I can use on them?

Yeah you make them at campfires with survival skill.

Good thing I tagged Survival, then.