Heck of a collection! That is a rough patch though, so many iconic villain firsts.
The closest I have to such a collection is Iron Man. Have 5.0 ToS 39 and Iron Man 1 through like... 600 or so across the various volumes. My Tales of Suspense collection is only about 12 books though. 😅
Haven't been collecting a ton lately though. Mostly indie stuff when I do. Obsessed with Usagi. My favorites are mostly 90s, early 2000s stuff that are short lived and easy to collect though. Battle Chasers, Warlands, stuff like that...
If I do go back for Marvel I think I'd prefer to concentrate on Daredevil.
Considering trying to sell off my Iron Man collection but not sure I can bring myself to do it.
My earliest ASM is #22. It is in pretty bad shape I think.