I see what you're aiming for. Here are a few ideas pluck out of the blue, but I don't know how feasible some of them are:
1) Have a "Realm of Chaos" province which is the only one that can build daemonic units. Make the population very small and grow very slowly so that it will limit the number of daemons able to be "recruited".
Problem: the Chaos player can just demob units in the province and boost its population. Perhaps something can be done with making it a long way away or make the daemon units take up lots more of the population than regular units. (I have to say, though, I quite like the idea of the Chaos player sending a trail of peasant units from the places he's captured back north to 'sacrifice' to get his daemon units)
2) Make your starting family members greater daemons, make them all infertile and so reduce the number the Chaos player will have.
Problem: I don't know if it's possible to make different generals have different models so they may all look alike.
3) Include a 'Daemon Prince' trait that can be gained by one of your characters so if they slaughter enough of the enemy they made a daemon prince/greater daemon. It you make it hard enough to get then it will necessarily limit the number of greater daemons in the army, on the plus side it will accurately reflect the fact that for Chaos hordes success breeds success. Or perhaps replace Faction Leader or Faction Heir, so there will only ever be (and always be) one daemon at a time.
Problem: I don't know if it's possible for the acquisition of a trait to change the general model, eg, if I made a special 'Scarface' version of a general could I mod the files so that any character who got this trait used the 'Scarface' version rather than the regular version.
But I have a question as well, for your greater daemon units, how are you getting around the 6 man unit limit?
Edit
Greater Daemon mercenaries!
Mercenary elephants only appear in a few places and have a very low refresh rate. Have a look at them in descr_mercenaries and see if you could put something similar in an isolated Realm of Chaos province.
Problem: Any other faction can recruit them too! But then again, if the other factions are getting banners into the Realm of Chaos province then Chaos is pretty much onto a loser anyway...
If you really want to be sure that no one else can recruit them, put the RoC province on an island within an inland sea (a Sea of Chaos perhaps

), ensure the only port for the sea is on the island and give the Chaos player the only ship in that sea.
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