The extra pin on ODP does nothing, should not be connected internally to anything either. It's sole purpose is to prevent ODP installation into typical 486 socket (without excessive force anyway).
The other way around, that is ODPR into ODP socket, that can be done, but Intel was "clever" and didn't want people doing it (and also wanted to sell expensive ODP/487 chips) so the pinout is slightly different. ODP has the UP output on B14, which is JTAG/TMS input on typical 486 (or NC). So it won't properly drive the FLT of the installed CPU. Well, this could be fixed by soldering a piece of wire but then ODP also has FERR on a different pin, because Intel realized this wire fix was too easy to do, so now two wires are needed.
So, is is possible to put ODPR into ODP socket? Yes, I've not tested it myself but I don't see why it wouldn't work. But you will need the mods to make it work. The UP->FLT mod is mandatory, or else both CPUs will be running and fighting for the bus. FERR is optional in the sense that the system will appear to work until some pre-486 code causes FPU exception. Well behaved 486+ code should not use FERR but rather let the CPU route the exception internally but I'm not sure at which point OSes started doing that. Anything DOS is obviously going to use the old method.
EDIT: Oh, I forgot to add that some Cyrix 486 and 5x86 CPUs might be using the otherwise unused pins, but then again an ODP socket should not be wired for Cyrix, so it should be safe.