A man in Ilex forest will teach your Pokemon the move
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I don't know all of the Pokemon that can learn Headbutt, but I know that Cubone can learn it.
Note: You need Headbutt.New Bark Town Headbutt Trees.CherryGrove City Headbutt Trees.search him on your pokedex and it will be red instead of green that means you need to headbutt a tree using headbutt.
Headbutt a tree in the Viridian Forest, you might also get a shroomish.
headbutt certain trees in mt.silver and I think on route 28.
I've never tried, but I DON'T Think so. Why not try it? If not, there's a man in Ilex Forrest that will gladly teach your Pokemon 'headbutt'