I assume the rear window defroster was working but could not clear the screen? You could see bars of clearer glass where the wires heat up? I am assuming the Alfa uses the standard multiple horizontal wire type rear defroster, not the multiple very fine vertical wire system used for front windshields. If the defroster is not working at all then that will be a fuse or wiring continuity fault.
It may not be a fault. If you can find a safe place to air the car out with the windows open, sunroof too, preferably in the cold then you can clear the humidity inside the car. If the problem recurs after you've verified your car interior is dry then most likely cause is a windshield leak. Modern cars have good air seals to improve performance of the hvac and reduce aerodynamic drag. If they get damp inside it can take a few days to dry out. This tends to show up first if your ambient temperatures drop suddenly.
Another method is to drive with windows partly open, particularly the rear windows, and the heat on MAX to dry out the interior. Do not use "RECIRC" in winter conditions or high humidity and cool ambient. Using the RECIRC function in cold conditions will cause rapid interior fogging that will not dissipate. It is remotely possible that your hvac was operating the AC (I assume you have automatic climate control). That can happen if you select too low a cabin air temperature when ambient conditions are cool and wet.
I note you're in the UK. Frosty windows are not usual in most of your country. Over here we routinely experience interior fogging (in my Jaguar and in my 164, even my SAABs) in very cold conditions even with the hvac operating correctly. If cabin occupants have snowy or damp clothing and footwear they can evaporate enough moisture to fog the interior glass. Most Canadians know this instinctively and brush off excess snow on clothing as well as kick snow off footwear as they enter a car, most knock their footwear on the sill tread in the door opening, for example. Knock snow or ice off your scraper before putting it in the car after use. In the cold and damp it takes very little extra moisture inside the cabin to produce the symptom you describe.
Eliminate the most likely causes before assuming a fault exists. If there is a fault it could be water ingress through a leaking windshield or door or sunroof seal. It could be the RECIRC function stuck on or activated unintentionally. It could be a coolant leak inside the heater (that should smell odd, though not necessarily familiar since Alfa no doubt uses long life coolant which does not smell like the old glycol coolant). Think of ways moisture might get into the car and eliminate those during winter conditions.