To spin while you have the puck, press L+Triangle.
To block a shot on defense, press L+Triangle without the puck.
If on defense and puckless, and you want to manually control the goalie, press L+Circle.
To block a pass on defense, press L+X.
When you're down by one late in the 3rd period, you'll need an extra man. In order to get 6 players on the ice, you'll have to pull the goalie and to do that ingame quickly, simply press the "Select" button.