you definitely want to paint the letters for exterior use. black expanded foam pvc turns chalky/grey, white discolors as well.
I've still slung them up unpainted and its "good enough from down here", but the unpainted faces have ALWAYS received complaints. Even had one set that was supposed to be temporary, discussed the known issue with the client, but they were only expecting to be in the tenant slot for under a year so it was "fancy-temporary", but cheap.... well, apparently there's also an odd interaction where the buildings across the street would block some of the sunlight most of the day, but cast a beam of light at the center of his building at the end of the day, leaving most of the letters unphased EXCEPT three letters in the center of a set of 30 degraded from UV exposure within a few months!
so if your intent is to have black face/white returns, then paint the whole letter white, face-up, and apply the black to a painted surface and you'll have no issue with longterm adhesion.