Question

Or does it come natural, and can toxic spikes and spikes work at the same time, if so, can stealth rock, spikes AND toxic spikes work at the same time? oh and if it learns it as an egg move, who does it have to breed with

Answer 1

Yes. pineco can only learn toxic spikes as an egg move. It can breed with Beedrill, skorupi, and drapion. (they can all learn it by leveling up.)

http://www.serebii.net/pokedex-dp/egg/204.shtml#toxicspikes