2) Atom Man vs Superman (Serial) - Lex
Luthor, yes, but technically not Lex. That serial came out in 1950, and Luthor's first name wasn't established as Lex until
Adventure Comics #271 in 1960.
It's notable, however, as perhaps the first time that a superhero adaptation outside the comics used a villain from the comics instead of an original villain, and one of the few times it was done in live action prior to
Superman: The Movie (the others I can think of being
Batman '66 and the first two episodes of the Lynda Carter
Wonder Woman). Although it somewhat conflated Luthor with the unrelated Atom Man villain from the Superman radio series, a post-WWII Nazi agent whose blood was infused with kryptonite and could fire deadly atomic rays.
6) Superman III - Ross Webster & a computer
And I still say Ross Webster felt more to me like Lex Luthor than the Reeve movies' Luthor ever did. (And the computer was originally going to be Brainiac.)
I will never personally understand the cries that always arise for Superman movies to feature also-ran villains instead of Lex.
Only a few of the many live-action Batman movies have featured the Joker. Only two Spider-Man movies have featured Norman Osborn as the Green Goblin. It makes sense to feature the #1 villain in a hero's debut movie, yes, but when there are a lot of movies, it's natural to want some variety.
And an "also-ran" character can always be turned into a star if used effectively. General Zod was a B- or C-list villain before
Superman II came out. Similarly, the Riddler had only been in a handful of issues before
Batman '66 made him a star on the same level as the Joker or the Penguin.
It's erroneous to assume that movies or TV shows depend on a comics character's prior popularity, because the movie/TV audience is far, far larger than the comics audience, so most viewers won't know or care whether a character was previously a big deal or not.
Besides, most of the live-action Luthors have been interpreted so differently, they might as well be different characters. Gunn’s movie may be the first time a version of the character clearly recognizable from the comics has appeared on the big screen since Atom Man vs. Superman. (TV has featured at least a couple more recently.)
I agree with your first sentence, though I think it's too early to judge the rest. The glimpse of Hoult's Lex in the trailer is certainly very promising, but we can't learn much from just a few seconds of screen time. Hoult looks effective in the role, but we've seen that a good performance can be undermined by poor writing (e.g. Cavill's Superman).