So excited to see Sam in the game!!!!! I'm Anne and I only play one person Sam knows, but not from the same universe- Carol Danvers. Carol has no idea who Sam is, but is getting to know the 616 people alright and knows something about her other self, but I'm sure she'd like to get to know him and will have questions. She's running the local bar (Pancho's) with Peter Parker from the Into the Spiderverse film.
I also have Miles Morales from the Spiderverse, who would be thrilled to see another African American here and probably have a lot of questions about his powers and what it's like to be Captain America! Might come to see Sam as a role-model, so there's that.
Next up is Obi-Wan from Star Wars. He's still figuring things out (he takes his time), and is sort of an outsider/hermit. He occasionally gets out and mingles, though.
Doctor 13 is the newest incarnation from Doctor Who. She'll have a lot of questions about any technology he has on and might try to scan him with her sonic. It's been a thing she's doing lately.
Finally, Harley Quinn. She's just arrived and wants trouble. If Sam rather avoid her (probably for the best), he can. But if he wants to try to stop or participate in a little chaos, she's looking forward to it!