To be awarded a penalty shot you need to be on “Breakaway" a breakaway is when one of your players is on his own (no other players between him and the goalie) and the other team commits a foul on him. The method below will help you put one of your players to be on a "breakaway". The reason this achievement is hard is that the AI players will usually go faster back to their goal, or will always be players in this area; you will do this by controlling the AI players to be behind you, commit a foul on you so you get a penalty awarded.
Make sure its All Star difficulty.
1. U need 4 Controllers! (possibly 3)
2. Put 3 Controllers for the other team (No difference what team you pick)
3. Increase the penalty shot slider (No need for any other slider)
4. Once the game starts commit fouls by the other team (just turn the right stick)To get 2 players (from the other team) kicked out in the box.
5. When 2 players are kicked out you are only left with 3 players 1 for each controller!
6. Push the other team players all the way to your Goalie (They well not go back because they are "humanly" controlled)
7. With any of your players go to the other team goal (you are now on a breakaway!) because all the other team is behind you.
8. Once you reach the goal - Click and keep holding the X (BLUE) - to be ready to shoot
9. Bring any of the other team players and use the right stick to commit a foul on this player.
10. Voilà, Penalty shot! ( All you need now is to actually score it!) Lowering the Goali sliders for HUMAN will help)
It works 100% no guessing involved you will ALWAYS get a penalty shot. Tried and experienced several times with several Teams. Got the achievement for myself and for couple of friends
I've added this photo, hopefully will help explain more on how to get it. I would have done a video, but i no longer have the game.