I was not very familiar with Daredevil prior to watching Season 1 of his Netflix series, and I found Kingpin's relationship with Vanessa, by far, to be the most interesting part of the plot. Credit goes to Vincent D'Onofrio for his nuanced portrayal of Wilson Fisk, but the underlying comic book story works as well. Families help to humanize villains, giving them credible motives for doing horrible things, while at the same time giving them a weakness that can bring then down either within or without. Kingpin's wife Vanessa sometimes was just a bystander to his evil plots:



Sometimes was the source of family drama through challenges to his criminal ambitions:



And sometimes was a pawn manipulated by both villainous and heroic foes to get the powerful crime lord to move in one direction or another:

Daredevil #180, during the original Frank Miller run.

Luthor, in the hands of Elliot Maggin was very nuanced, especially in his two Superman novels. Maggin really got inside his head and showed him to be more than a "Mwa-ha-ha" villain, like in Challenge of the Superfriends. The guy sleeps in a sarcophagus, on Snoopy sheets! He worships Einstein, Clark Kent was his best friend, in Smallville, and he uses a string of identities to create and hide various scientific deivces and inventions. He travels the world as a crusading doctor, finding miracle cures for diseases, while also staging theft of scientific documents. Maggin also wrote a more rounded supporting cast, especially Lois and Steve Lombard, the sportscaster who attempts to bully Clark.

Ra's al Ghul, in Denny O'Neil and Mike Barr's hands was always more of a "t'weener." Many of his plans would greatly improve the world, even if a portion of the population had to die to achieve it. He is honorable and willing to stop worse evil. He's a more balanced version of Fu Manchu (who inspired the character).

Nash, the new Mist, in James Robinson's Starman was a fascinating character. Verbally abused by her father, in love with Jack, until he kills her brother Kyle, the only one who was kind to her and showed her love.

Johnny Bates, in Alan Moore's Marvelman is another: the child sidekick who grew up as the most powerful man on the planet and became a monster because of it. Literally inside him is a small, frightened boy, who had been trapped for 20 years.

Darkseid, in Kirby's hands, was quite complex, remarking of the nobility of foes and carrying a forbidden love, that led to his lover's murder, on order of his mother. He is very operatic in many ways.

Will Eisner's femme fatales could be quite interesting and layered, especially Sand Saref, who inspired Elektra. P'Gell was a little more straightforward; but, always fun and always more playful than evil.

Dr Sivana and Black Adam have had their moments. Sivana, especially early on, when his origin was revealed, was actually a bit sympathetic, though, mostly, he was a cackling baddie. Black Adam was more nuanced at DC than Fawcett, as they dwelt more on how he was seduced by power, rather than just throw that out as to him being evil.

That's a really nice primer for people just coming to the character. I was there for ASM 197 as well as the return of the Kingpin during the Miller run, which is a Master's Class in rehabilitating a tired, cliched character and positioning him as a modern, major threat. Miller Daredevil is good comics and essential for a healthy reading diet.

I keep meaning to re-read read Maggin's Superman novels, as I haven't read them since they were first published (when I was all of about 12-13 years old). I don't remember too much about them, but what does stick in my memory is the really good characterization of Luthor.