It's both a change and an improvement. The themed widgets can be used in
conjunction with the traditional widgets, but in many cases it's
possible (and desirable) to update your entire application to use the
themed widgets.
PMW is certainly a helpful addition to the Tkinter developer's toolbox,
but it also has limitations. It suffers from some of the same
limitations as Tk itself, i.e. it is rather dated in appearance, and
even it lacks some modern UI features such as a good multicolumn
listbox, treeview, etc. In addition to the ttk themed widgets, other,
more configurable pure Tk-based megawidget packages exist, such as
BWidgets and Tablelist, and there are Python wrappers for these at the
Tkinter wiki (
http://tkinter.unpythonic.net/wiki/).
Another book I've found very helpful for learning Tkinter is Programming
Python by Mark Lutz--a lot of coverage there of GUI development.
--Kevin
Another possible consideration when choosing a GUI to learn Python -
will you want to print from within your GUI application? Admittedly, I
haven't looked to see whether this situation has changed or not for
some years now, but a GUI based on Tkinter (whether it is ttk or Pmw
or whatever) has no support for "printing". Other GUI frameworks, such
as wxPython, Jython, PyQT etc have API's that allow printing of
information from within your GUI application.
Now if you go the Tk route, I am sure you can use the Win32 bindings
to do printing - but I personally could never work them out

Maybe
there is some reasonable documentation or example code for doing that
these days - but there wasn't when I first approached the problem
(which was back in the python 2.1 days - ancient history!). Printing
using Windows API was a complete mystery to me.
My first GUI application required information to be printed out - I
wrote the whole thing using Pmw and Tkinter - only to find that I had
no way of getting stuff to a printer (I was learning Python and
Tkinter at the time

). I briefly explored "porting" my application
to wxPython or Jython because both frameworks provided printer API
functions - at that time, PyQT was commercial license only for a PC,
so that wasn't an option. I found wxPython stunningly hard to
understand from the documentation (I have since purchased wxPython in
Action by Rappin and Dunn but have never found the time to read it). I
had some problems porting the code to Jython (my code relied heavily
on the pickle module and Jython had some severe bugs in that area at
the time), so in the end I came up with a fairly micky-mouse system
that placed information that required printing into .txt files and the
GUI application started Microsoft Word using mail-merge templates and
I got the information to the printer that way - not ideal! But it
worked
So consider that in your decision process - maybe somebody can
(kindly

) hop in here and say "that's easy, just look at xyz or
read this book abc" to find out how to print from within an
application using Tkinter.
Regards
Peter