That might work for decanting paint from a spray can for airbrushing or touching up with a brush, but I'd advise against trying to actually paint something using that method.
Also, you may note that when you spray WD-40 "straight" without the extension, you get the usual fine mist, but when using the extension it can often be less finely atomised, stream-like and "splattery" .
Definitely not a good idea.