Reminds me that the most valuable comic book I've ever owned (which I bought at a flea market at age 13, when I had no idea what I'd put my grubby paws on) was the first time Spidey fought Doctor Doom. And did a bang-up job of it, if I remember right. I think it was Amazing Spider-Man #5, probably published in 1963. I don't have it anymore. Anyway. . .
I do think it's interesting that Spidey villains are so rare to show up in other titles. Especially considering that he rivals Wolverine for being a Cameo whore. And his rogues gallery is huge, and fairly iconic. But regardless how powerful they are, his enemies usually aren't trying to take over the world, I guess.