You could begin with 'Ultimate Spider-Man'. It has a modern take and is easier to follow for new readers. The storylines are engaging and accessible.
I'd recommend starting with 'The Amazing Spider-Man'. It's a classic and provides a great introduction to Spidey's world.
I think 'Spider-Man: Homecoming Prelude' is a good choice to start. It ties in with the movie and gives a fresh perspective on the character. The art and writing are appealing to newcomers.