Second version is obviously more readable because you added another shade. It is not too highlighted yet to me, quite the opposite but that kind of thing should be judged against the scene, and depending on the level of focus you want on him I guess.
If you want to show more volume like in the second piece without making him generally brighter, then I think some dramatic underlights would fit very well. Can't think of anything else, but I am sure others here will have different suggestions for him.
Ah, to keep him more Spidey I would change his tophat into a bowler hat, so his head keeps rounded and more easily indentifiable coupled with the spidey eyes. I didn't knew it was Spiderman until I read your description