One of my faves is 'Coming Home' , which is where he goes up against a really big threat to him personally, because of who he is (Spiderman), and its a turning point for him because his life is changing so much - with regards to his family life, his relationships etc - it also shows you the sort of hero he is. If you want to 'catch up' for the movie - the new Ultimate Spiderman is good - get the TPBs; its basically the re-telling of the story updated for modern day, with the odd change here and there - its also rather funny too

The good thing about Spideys character, is that he's always been the same person - not like Batman being nice, being a dark loner, being nice etc - he's just the normal guy who got all these powers, so it doesnt make it that difficult to get into his head - as he's fairly consistant.