The unlockables I typed below can be also used on the PlayStation 3 version. If you have any trouble on understanding how to unlock, you can find it on your game. On the Main Menu, go to "Gallery" and then "Historial", after that press some times the LB or RB, in order to go to the right menu.

Effect	How to unlock
Classic Argentina	Win the World Cup with Argentina
Classic Brazil	Win the World Cup with Brazil
Classic England	Win the World Cup with England
Classic France	Win the World Cup with France
Classic Germany	Win the World Cup with Germany
Classic Italy	Win the World Cup with Italy
Classic Netherlands	Win the World Cup with Netherlands
Classic Players 1	At the Master League, win the Division 1 League
Classic Players 10	Win the European Cup
Classic Players 11	Win the African Cup
Classic Players 12	Win the American Cup
Classic Players 13	Win the Asia/Oceania Cup
Classic Players 2	At the Master League, win the Division 1 Cup
Classic Players 3	Win the European League
Classic Players 4	At the Master League, win the European Cup
Classic Players 5	Win the England League
Classic Players 6	Win the France League
Classic Players 7	Win the Italy League
Classic Players 8	Win the Netherlands League
Classic Players 9	Win the Spanish League