1. Did we ever get this tag team pairing? Even a Coliseum Video one-off or something?

2. Who plays babyface-in-peril in this partnership?

1.  I wanna say that yeah, they teamed up on a Toronto house show that was on Prime Time?  

Yes, that is indeed the case:

21.04.1985 World Wrestling Entertainment Ricky Steamboat & Tito Santana defeat Brutus Beefcake & Greg Valentine (15:31)

WWF Prime Time Wrestling – TV-Show @ Maple Leaf Gardens in Toronto, Ontario, Canada

They also teamed up a bunch of more times in 1985, primarily against Muraco and Fuji. 

2.  Steamboat.  Tito is the clear hot tag guy in that scenario.