From the Main Menu, select Game Modes>Penalty Kicks. To unlock this achievement, you must score on all of your penalty kicks. There will be five rounds in the shootout. You just need to score on all of your kicks, even if the shootout only lasts 3 rounds or goes past 5 rounds. This will take a little practice to find a technique that works for you. For me it was holding the joystick either just left or right of straight up. Then shooting (with A button) between half and full power. Remember to play goalkeeper as well. If you score on all of your first three shots and save all of the other teams three shots, the achievement unlocks.