Rather than using a dictionary, consider this:
playerName = ['a', 'b', 'c', 'd', 'e', 'f', 'g', 'h', 'i', 'j', 'k', 'l', 'm']
playerScore = [12, 15, 31, 26, 94, 13, 16, 12, 11, 85, 70, 14, 56] 
player = sorted(zip(playerName, playerScore), key=lambda x: x[0])
print(player)
[('a', 12),
 ('b', 15),
 ('c', 31),
 ('d', 26),
 ('e', 94),
 ('f', 13),
 ('g', 16),
 ('h', 12),
 ('i', 11),
 ('j', 85),
 ('k', 70),
 ('l', 14),
 ('m', 56)]
Just call python's inbuilt sorted function and pass a lambda function as a parameter so it knows what to sort on.
If you want to construct an ordered dictionary, you could use collections.OrderedDict (python < 3.6):
from collections import OrderedDict
player_dict = OrderedDict(sorted(zip(playerName, playerScore), key=lambda x: x[0]))
print(player_dict)
OrderedDict([('a', 12),
             ('b', 15),
             ('c', 31),
             ('d', 26),
             ('e', 94),
             ('f', 13),
             ('g', 16),
             ('h', 12),
             ('i', 11),
             ('j', 85),
             ('k', 70),
             ('l', 14),
             ('m', 56)])
It's still a dictionary, and supports all dict methods:
print(isinstance(player_dict, dict)
True
Note that dictionaries in python3.6+ are ordered by default, so just pass a list of tuples from sorted to dict and you'll get the same sorted result.