In the Rhino's first appearance ASM # 41, Spidey just wore him down, constantly slamming Rhino head first into hard objects, finally flipping him head first into the pavement, knocking him unconscious.
In their second fight, working with Curt Connors Spidey developed an additive to his webbing that dissolved Rhino's synthetic hide.
In the Ult. Spider-man game he fought him with the help of some quick drying cement, a wrecking ball and an open power source on the Rhino's back.
In the 90's cartoon I remember he used the symbiote costume to overpower him. This was also when he realised that the suit was amplifying his anger as well as strength as he stopped himself from splatting the Rhino with a very large steel door.