For your first part of the question, you can left align and use a space as the fill char using a width of 12:
'%-*s' % (12, '##') can be replaced with '{: <12}'.format('##').
For the second part no you cannot specify the fill character with old style formatting.
There is a nice site here that shows most of what you can and cannot do with old vs new, a snippet that covers Padding and aligning strings:
Padding and aligning strings
By default values are formatted to take up only as many characters as needed to represent the content. It is however also possible to define that a value should be padded to a specific length.
Unfortunately the default alignment differs between old and new style formatting. The old style defaults to right aligned while for new style it's left.
Align right:
Old '%10s' % ('test',)
New '{:>10}'.format('test')
Align left:
Old
'%-10s' % ('test',)
New
'{:10}'.format('test')
By argument:
In the previous example, the value '10' is encoded as part of the format string. However, it is possible to also supply such values as an argument.
Old
'%*s' % ((- 8), 'test')
New
'{:<{}s}'.format('test', 8)
Again, new style formatting surpasses the old variant by providing more control over how values are padded and aligned.
You are able to choose the padding character:
This operation is not available with old-style formatting.
New
'{:_<10}'.format('test')
Output
And also center align values:
This operation is not available with old-style formatting.
New
'{:^10}'.format('test')