Make Pip detect Pip/Python mismatch

I don’t think merging the paths would not even help much.

A simple scenario:
Install Python 3.X. Add it to PATH.
Install Python 3.X-1. Add it to PATH.
pip probably refers to 3.X-1 because it was added to PATH last.
py probably refers to 3.X because it prefers the latest version.

Probably not everyone uses that. Nothing enforces them to remain in sync. The order of the paths in PATH also matters.

Some more (complex) reasons for a mismatch are mentioned here: