Python 3.3 introduces Python Launcher for Windows that is installed into c:\Windows\ as py.exe and pyw.exe by the installer. The installer also creates associations with .py and .pyw. Then add #!python3 or #!python2 as the first lline. No need to add anything to the PATH environment variable.
Update: Just install Python 3.3 from the official python.org/download. It will add also the launcher. Then add the first line to your script that has the .py extension. Then you can launch the script by simply typing the scriptname.py on the cmd line, od more explicitly by py scriptname.py, and also by double clicking on the scipt icon.
The py.exe looks for C:\PythonXX\python.exe where XX is related to the installed versions of Python at the computer. Say, you have Python 2.7.6 installed into C:\Python27, and Python 3.3.3 installed into C:\Python33. The first line in the script will be used by the Python launcher to choose one of the installed versions. The default (i.e. without telling the version explicitly) is to use the highest version of Python 2 that is available on the computer.