Defeating Rhino
To defeat Rhino, all you have to do is jump. While you are in the air, press L. Then, wait for him to run into the wall and get some combos on him. When he runs into the next room, do the same. Run around the poles when he gets the big pipe.
Defeating Shocker
To defeat Shocker, you must let Rhino knock down the platform he is standing on (see the "Defeating Rhino" hint). Then, lock in on him with the Spidey target and either blind him or hold L and press Triangle. Keep doing that and try not to die.
Defeating Vulture
Stay in the construction area on top of the building. Remain in between the two buildings that Vulture cannot get to you. After awhile, his health will get down to green. He will land, and this is when you can attack him. Do it quickly; you only get five to ten seconds to punch him.