The ones i've flown for real Innsbruck is the most fun (normally go visual down the valley, but the one time i went to minima on that approach in a snow storm concentrated the mind!) Nice is very scenic, the Riviera visual particularly. Marseilles involves lots of changes of direction and Beacon and can be quite busy. Still think the approach to LHR at dusk or dawn takes some beating for views!
Also try spitzbergen in flight sim if you can find charts