Only a handful of Superman's villains(especially in the post-Weisinger, pre-CRISIS era) crossed over into other media(Luthor, Bizarro, the second Toyman, and-I think-Brainiac, as part of the Legion of Doom on CHALLENGE OF THE SUPERFRIENDS).

As far as the comics are concerned, I've mentioned in other threads my opinion of Martin Pasko's writing, as opposed to Cary Bates. Pasko was, better at action-oriented supervillain stories, while Bates, IMO, relied on 'softer', science-fiction oriented plots. When he did use villains, they didn't have as much of an 'edge' as they did under Pasko's control.

Pasko could make guys like Terra-Man or Vartox interesting. Under Bates, they were merely the pale imitations of the celebrities they were parodying.

One of my favorites was this issue, which had a nifty twist to the story...

With Superman, I remember a lot more stories that didn't have villains at all. It seems like most of his stories were about Lois getting super-powers, or discovering another lost survivor of Krypton, or Jimmy getting super-powers, or Superman's Big Brother, or Lois scheming to uncover his secret identity, or an "imaginary story". Looking at the covers of Superman comics from the 50s and 60s, it's hard to even spot Luthor or Brainiac amid the forest of one-shot foils.

I don't think the problem is that Superman's villains are less inherently interesting than anyone else's. I just don't think they got used often enough to make them as memorable.

Regarding the use of villains, Superman stories of the late Golden and Silver ages were more often than not puzzle stories, presenting a problem for Superman (and thereby the reader) to try to figure out rather than concerning themselves with character conflict, drama, knock-down, drag-out brawls or high-flying action. There was a great deal of imagination and story invention with new supporting characters, devices, and what not, but little in the way of emotional involvement or character-motivated drama.

In such stories, there isn't much for the villain to do when the main problems are usually the result of Lois' scheming or Jimmy's bumbling. Also, aside from the Luthor-Brainiac team or the occasional Prankster and Toyman combo, Superman's villains didn't socialize much. For organized wickedness, there was the Superman Revenge Squad and later, "The 100," "Skull," and "HIVE." 

A brief assemblage of Superman foes appeared in issues #417 and #418, including Grax (A Jim Shooter created foe with a 20th-level intellect who treated Brainiac like a moron), Luthor (in a seldom seen gray, black, and orange costume), Brainiac, and the Marauder.