In another thread someone already said the usual 6 unlockable classic teams are there.
Argentina,Brazil,France,England,Germany and Netherlands im unsure if these are unlocked through the pes shop or if you have to win the world cup with said country.
Normally the unlocked players are the likes of Rai,Garrincha,Dalglish,Savejevic,Stoichkov,Laudrup etc though the lineup could obviously change on this years edition.