I've certainly seen polyfilla used in this way (it doesn't seem to shrink, crack or fall out and can be painted OK.) However, polyfilla produce dozens of products, so I'd suggest going to polycell.co.uk and checking out the specific one you have. If they say it's OK, it's OK.
You don't need to completely sand down gloss, but I'd say sand it down as best you can rather than a "quick once over" (paint won't adhere well to a high gloss finish.) Prime the whole thing, de-nib (i.e get rid of any bits trapped in the paint) and then paint over it.