The rule is simple, Win will attempt to locate:
- Executables (when not launched with full path)
- DLLs (loaded (recursively) by executables)
in the directories from %PATH% in the order that they appear.
References:
A MinGW version is stand alone (it doesn't depend on the other), so if all its dirs are in %PATH%, it will be chosen automatically, and the 2nd version is simply going be ignored therefore its presence in %PATH% is useless (actually, it will add additional overhead when the OS will search those dirs too).
However, if dirs from the 2 versions are inserted interleavedly (some dirs from 1st version, some from 2nd version, some other dirs from 1st version, ...), then you might (and most likely will) get in trouble, so don't do it.
I guess you need both variants to generate 064bit and 032bit binaries.
But doesn't GCC's -m32 argument do the trick?
In short: there are some situations when it's OK (to have both versions in %PATH%), there are others when it's not. But, in any case, having the 2nd version will come with no benefit.
On a related topic, check [SO]: Python Ctypes - loading dll throws OSError: [WinError 193] %1 is not a valid Win32 application (@CristiFati's answer) for details about mixing processes and .dlls built for different architectures.