You must defeat these CPU inside story mode 3 times (or more) each; Eiki, Gate Mace, Key Mace, Key Mace #2, Zape.
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There are various different ways to unlock packs. Try beating everyone you come across 3 times. That should unlock a lot. Some can only be unlocked through story mode. Look on gamefaqs.com. That should tell you more.
Neither the card nor the duelist are avalible in 2007. Strangly the duelist is but not the card in 2008. You can unlock her (yes, it's a she) by clearing the Phantom of Chaos Armytile stone challenge in the World of Chaos.
Defeat the following duelists 3 times each:Barclay, Shuji, Taniyama, Ellison Noula, Skathi, Yagishita, Geruzet,Motoi, Kyono, Fudagawa, Dio, Vega
some of your allies have specialization in an area like Alistar's specialization is being a templar to learn ones of your companions get their approval of you up and you may learn it from them. Others may be found all over Ferelden like the Duelist go to the pearl brothel and you see a woman fight, after she wins talk to her and ask to learn from her. she will play a game with you first and you use dexterity and see that she is cheating. then you unlock the duelist specialization. google the locations of the others if you want them and dont forget to select what you want to specialize in when you level up. its under the your character's picture.