I can't believe it's been 20 years since Spider-Man was released, I still remember organizing a mass outing for me and a bunch of my college buddies to go see it on opening day. Absolutely loved it, and still do.
Stacking up the superhero movies of that era though (no way I'll even try to compare them to the current MCU or Bale's Batman), I'd rank it:
X-Men 2
Spider-Man 2
Spider-Man 1
What bumps Spider-Man 2 just a bit above 1 was how great Alfred Molina was as Dr. Octopus. Older me really came to appreciate the meeting he and Tobey Maguire had prior to the fusion experiment in his loft. The dialogue exchange really humanizes the character and makes him likeably tragic, even in the worst throes of his villainy. It wasn't quite as easy to do that with Dafoe, because he's just naturally a little weird and creepy.