Typography experts agree: Typewriter quotes in non-code text bodies are wrong.1, 2
I gather that PEP editors might not be willing to learn how to input typographically correct quotes.
If this is case, I propose to start using smartypants or similar code to automatically convert typewriter quotes and apostrophes into curly ones. Smartypants works on HTML and skips <code/>, <pre/> and other literal tags.
I would prefer to directly have curly quotes in the rST document, as “direct” is more readable than “escaped”, while explicit is better than implicit (and smartypants could find false positives, although unlikely).