I actually just thought of an interesting solution. While Windows will not allow you to easily alias programs, you can instead create renamed batch files that will call the current program.
Instead of renaming the executable which will break a lot of thing including pip, create the file python2.bat in the same directory as the python2.exe. Then add the following line:
%~dp0python %*
What does this archaic syntax mean? Well, it's a batch script, (Windows version of bash). %~dp0 gets the current directory and %* will just pass all the arguments to python that were passed to the script.
Repeat for python3.bat
You can also do the same for pip and other utilities, just replace the word python in the file with pip or whathever the filename. The alias will be whatever the file is named.
Best of all, when added to the PATH, Windows ignores the extension so running
python3
Will launch the python3 version and and the command python2 will launch the python2 version.
BTW, this is the same technique Spyder uses to add itself to the path on Windows. :)