I don't know how familiar you are with the comic history of the character, or the storylines of the last say 5 years, but here are some of my favorites new and old, and all should still be available in trade form..
Red-Headed Stranger
24/7
Kraven's Last Hunt
Kraven's First Hunt
Election Day (Character Assassination arc)
Grim Hunt
Shed
Brand New Day 1-3
Spider-man Legends: Todd McFarlane 1 & 2
Spider-man: Identity Crisis
Origin Of The Hobgoblin (JR Jr. art, but well worth a look)
Revenge Of The Green Goblin
Spider-man: Back In Black books 1 & 2
Friendly Neighborhood Spider-man book 2: Mystery Date
Return / Revenge Of The Sinister Six
Spider-man: Noir (book 1)
Spider-man 2099
EDIT: and I'd be remiss if I didn't mention two works that are very hated here, but that I liked--Spider-man / Black Cat: The Evil That Men Do, and Marvel Knights Spider-man #1-12..



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