I have attempted to do research on this subject but I have been unable to find anything because I don't really know how to phrase my questions. I am just starting to make a Python application and the first thing that I want to get straight is appearance. For the appearance of the program, I want to have my own custom close button, maximize button, minimize button, and bar at the top as I have done in the past with Expression Blend. How can I do this with Python, and what graphics library(Tkinter, etc.) should I use? Thanks.
Check out wxPython for a start, it's widely used.
If you're interested in Qt, check out both PySide and PyQt.
If you're talking about Windows only, rather than cross platform, consider PyWin32 to use the Windows APIs directly instead of through one of the other packages.