Two reasons I can see:
Hot air rises - therefore, the best way to quickly warm up the whole car is to bring the hot air in as low as possible, i.e. at your feet. So if it's cold, you're better off using the foot setting than the face setting, which might quickly warm your face but not the rest of you.
The hot air blown at the windscreen will also deflect off the glass towards your face, thus warming your face, and making extra air blown in that direction less necessary.
As for why the setting isn't available, that's actually fairly simple if you look at how the vents tend to work - or at least, how they used to work (I suspect more modern vehicles have electronic controls rather than a mechanical linkage).
On a mechanical system, you don't really have five settings at all, but three - windscreen, feet, face. The output is then controlled by a sliding input vent that lines up with these. To get the intermediate settings, you simply slide the vent halfway between two of the outlets. Because of this, you can't have a position that's halfway between the third and first options - so only two of the half and half options are available, and someone, historically, chose the two that were most useful. The reason it's still done now is, indeed, because that's how it's always been done.
----------------------------- |---------------
Air in -> -> Windscreen -------------- -> Windscreen
----------------------------- Air in -> ---------------
| -> Feet -------------- -> Feet
|---------------- |---------------
| -> Face | -> Face
|---------------- |---------------
If you'd like to see it in more detail, have a look at episodes 16 and 17 of "Project Binky" on Youtube, where they show the build of a custom HVAC system for the car in some detail.