The third (or was it fourth?) volume in the Marvel Origins trades (preceded by Origins of Marvel Comics and Son of Origins, and followed up by The Superhero Women) features the villains, natch, including Cap's arch-foe the Red Skull!
One of the Simon and Schuster paperback collections here... I used to have it, but it's been long gone, so I don't recall what's in it. Unfortunately, the Grand Comics Database doesn't seem to have the book indexed!
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