Writing a program that accepts a two digit # that breaks it down

Try this:

val = raw_input("Type your number please: ")
for i, x in enumerate(val, 1):
    print "#{0} digit is {1}".format(i, x)

It was not clear from your question whether you are looking to use % for string substitution, or % for remainder.

For completeness, the mathsy way using modulus operator on ints would look like this:

>>> val = None
>>> while val is None:
...   try:
...     val = int(raw_input("Type your number please: "))
...   except ValueError:
...     pass
... 
Type your number please: potato
Type your number please: 27
>>> print 'The first digit is {}'.format(val // 10)
The first digit is 2
>>> print 'The second digit is {}'.format(val % 10)
The second digit is 7