Personally, if Jennifer Walters got to know Peter Parker in the same manner as Carol Danvers, they would become fast friends. Jen's likes being the She-Hulk because it represents her confident side that she has a hard time showing in her shy human form. But I think that her shy human form would be a good fit (whenever Jennifer is around Peter Parker) because Peter could actually make her feel like the She-Hulk without the need for her to transform into her altered ego. I am not sure if Wyatt Wingfoot was able to do that; and John Jameson wasn't able to convince her to stay in her human form during their marriage for him to do so. And the only reason why Peter might be able to make Jennifer use her human form whenever they are out together is because his radioactive blood affects her ability to retain her sensational She-Hulk form(Not only that; but Peter's radioactive blood heat signature would make the She-Hulk vulnerable towards it because it could cause her to permanently evolve into the Incredible She-Hulk(Jennifer's final Hulk incarnation). But her human form is immune to those affects. The twist about this situation is whenever Jennifer uses her human form around Peter Parker, it makes her STRONGER as the She-Hulk. Love is a very powerful weapon!!!!
I feel that if Jennifer were to start a relationship with Peter Parker/Spider-Man, it might turn out to be one of her best relationships. Although it would come at a price, meaning that Jennifer would no long be the Sensational She-Hulk, but rather the Incredible She-Hulk, of which Jennifer still retains her intellect and is able to revert to her human form.
But in a match up between Spider-Man x She-Hulk, Jennifer would win because Spidey's Radioactive Blood would cause her to transform into the Incredible She-Hulk. Peter's radiated blood would cause Jennifer gamma radiated blood to mutate into her final She-Hulk evolution. And it would be all Spider-Man's fault.
What would be more interesting is the notion that Jennifer Walters actually befriended Peter Parker before she become the She-Hulk. That in itself would make things interesting. Imagine if the spell that Dr. Strange placed upon Peter to make the world forget that he's Spider-Man actually revive Jennifer's protection spell that makes people forget that she's the She-Hulk(whenever she's in her human form). It might be interesting to see the benefits of Jennifer's outing with Peter Parker in her human form actually makes her stronger as the She-Hulk, which might allow her to tap into her Savage/Incredible She-Hulk form while still retaining control of those powers for a short time. In addition, Peter might be one of the guys who would make Jennifer feel like the She-Hulk without her having to transform into her whenever they go out together on occasion. This is one reason that I would love to see Jennifer know Peter Parker as just himself and not as Spider-Man(in the same manner as Carol Danvers, for example) because we would see a very good dynamic to their friendship that would be in-depth to both their normal lives and personal struggles.