If I understand correctly, I'd probably go with a list, then use pattern matching to add up cards values and search for specific types of hands according to these rules. Example:
import random
#types of cards reference: Heart, Spade, Diamond, and Club.
cards = ['1h','2h','3h','4h','5h','6h','7h','8h','9h','10h','jackh','queenh','kingh','aceh',
'1s','2s','3s','4s','5s','6s','7s','8s','9s','10s','jacks','queens','kings','aces',
'1d','2d','3d','4d','5d','6d','7d','8d','9d','10d','jackd','queend','kingd','aced',
'1c','2c','3c','4c','5c','6c','7c','8c','9c','10c','jackc','queenc','kingc','acec']
#card values
value = [1,2,3,4,5,6,7,8,9,10,13,12,11,14,
1,2,3,4,5,6,7,8,9,10,13,12,11,14,
1,2,3,4,5,6,7,8,9,10,13,12,11,14,
1,2,3,4,5,6,7,8,9,10,13,12,11,14,]
#shuffled deck of cards
deck = ['1h','2h','3h','4h','5h','6h','7h','8h','9h','10h','jackh','queenh','kingh','aceh',
'1s','2s','3s','4s','5s','6s','7s','8s','9s','10s','jacks','queens','kings','aces',
'1d','2d','3d','4d','5d','6d','7d','8d','9d','10d','jackd','queend','kingd','aced',
'1c','2c','3c','4c','5c','6c','7c','8c','9c','10c','jackc','queenc','kingc','acec']
#shuffle the deck
random.shuffle(deck)
#player 1's hand
hand1 = []
#player 2's hand
hand2 = []
#pass out 5 cards to players
for a in xrange(0,5,1):
hand1.append(deck.pop(0))
hand2.append(deck.pop(0))
#player 1's score
player1 = 0
#player 2's score
player2 = 0
#add up card values to calculate scores
for a in xrange(0,5,1):
player1 += value[cards.index(hand1[a])]
player2 += value[cards.index(hand2[a])]
print player1,player2
if player1 > player2:
print "player 1 wins!"
elif player1 < player2:
print "player 2 wins!"
elif player1 == player2:
print "its a draw!"