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I think it would work better with Oblivion characters to be honest.
But for Skyrim:
Ulfric - King
Torrygg - King
Tullius - King
Alduin - Ace of Spade
I did one before for lulz. Not a whole lot of thought went into it:
http://www.gamesas.com/topic/1445535-i-think-i-play-this-game-too-much/
another name for a "Jack" playing Card is a "Knave", which was a title used for Male Servants of Royalty (this could be anything from an Adviser to the King, to the predecessor to a Butler)..
as for Skyrim themed cards... we gotta throw in Delphine for Queen of Spades...
Ace of Spades = LDB & Miraak
Ace of Clubs = Alduin
Ace of Diamonds = Hermaues Mora
Ace of Hearts = Arch-Curate Vyrthur
King of Spades = Lord Harkon
King of Clubs = Ulfric Stormcloak
King of Diamonds = General Tullius
King of Hearts = Paarthurnax
Queen of Spades= Serana & Frea
Queen of Clubs = Maven Black-Briar
Queen of Diamonds = Elenwen
Queen of Hearts = Jarl Elisif
Jack of Spades = Neloth
Jack of Clubs = Odahving
Jack of Diamonds = Delphine
Jack of Hearts = Knight-Paladin Gelebor
Joker = Sheogorath & Cicero
I'd say the Diamonds suit should be Imperials, the Clubs should be Stormcloaks, the Spades should be notable enemies, and the Hearts should be notable allies. The exceptions being the Aces, which are four of the Divines.
Red Joker: Cicero
Black Joker: Sheogorath
Ace of Spades: Arkay
Ace of Hearts: Mara
Ace of Clubs: Talos
Ace of Diamonds: Akatosh
Spades:
King: Alduin
Queen: Miraak
Jack: Harkon
10: Hermaeus Mora
9: Ebony Warrior
8: Mercer Frey
7: Ancano
6: Mirmulnir
5: Madanach
4: Falmer Nightstalker
3: Draugr Deathlord
2: Bandit Chief
Hearts:
King: Paarthurnax
Queen: Jarl Balgruuf
Jack: Arngeir
10: Delphine and Esbern
9: Master Neloth
8: Farkas, Vilkas, and Aela
7: Arch-mage Savos Aren
6: Brynjolf/Karlia
5: Dark Brotherhood Assassins
4: The Housecarls
3: The Hirelings
2: Hold Guards
Clubs:
King: Ulfric Stormcloak
Queen: Galmar Stone-Fist
Jack: Ralof
10: The Gray-Manes
9: Ysarald Thrice-Pierced
8: Thongvor Silver-blood
7: Laila Law-giver
6: Dengeir of Stuhn
5: Wuunferth the Unliving
4: Thorald Gray-Mane
3: Stormcloak General
2: Storncloak Soldier
Diamonds:
King: Titus Mede
Queen: Elisif the Fair
Jack: General Tullius
10: Hadvar
9: The Battle-borns
8: Legate Rikke
7: Amaund Motierre
6: Maven Black-briar
5: Brunwulf Free-winter
4: Jarl Igmund
3: Imperial Captain
2: Imperial Soldier