In JMS’ run on “Amazing Spider-Man”, they had been building up a close relationship between Peter and Stark over the couple of years prior to Civil War: Peter got a job at Stark industries and Aunt May and Mary Jane moved into Avengers Tower after May’s home got destroyed by an enemy of Spider-Man (this was also around the time that Spidey joined the New Avengers).
The Peter/Tony relationship was a nice development that felt pretty natural and led to the tech-enhanced red-and-gold suit. And of course, it made their falling-out in Civil War all the more powerful if you had invested in those earlier stories.
For that reason, I’d say that if you’re going to check out any of the CW tie-ins, it’s the JMS Spidey stuff leading up to and during the event that’s most worth it. It enriches the main story quite a bit.