Essential Spider-Man Vol 1.
It includes Amazing Fantasy 15, the first 20 issues of the series plus the first annual. It's pretty amazing-pun intended---with what Lee and Ditko did in these earlier issues. They had the character down right from his first appearance and introduced most of his rogues gallery in the first year of his existence. You get the first appearances of Doc Ock, Vulture, Lizard, Sandman, Electro, Mysterio, Green Goblin, Kraven and Scorpio. You get the first appearance of the Sinister Six too.
The tone is set right from the beginning with plenty of Peter Parker, Aunt May and his supporting cast at school. You're reminded that his first crush is actually Betty and not Gwen and the basic dilemma of a young man balancing everyday life with the responsibility of superpowers. The heart of Spider-Man is all there.