An army vs a demon prince
What a neat idea!
I might make a suggestion.
The PC's are going to bring an army. They plan to cheat.
The primordial demon lord is also going to bring an army. He's a primordial demon lord, of course he's going to cheat.
The two armies should cancel each other out. The battle will then be decided by the PC's actions.
So lets look at your steps.
A. PC's open portal. It's meant to devastate the area, allow a giant unstoppable army to come through, and materialize the demon lord. The challenge for the PC's is to mess it up. Successes here can give them a variety of bonuses:
1.Creating (and identifying) safe zones: PC's and allies that stand there are missed by the wash of demonfire or lightning that erupts from the portal.
2.Limiting the demonic army. Maybe instead of all of it appearing on round one, it appears over 10 rounds...each round another force comes in. Maybe the portal is too small for a fat hezrou or nalfeshnee, and only small dretch, quasits, and larvae can come in.
3. Limiting the demon lord. Maybe the demon lord is restricted to a few small squares, or he comes in as a lower power avatar instead of as his full self. Maybe he's buried in the ground up to his waist, so he's restrained, or immobilized.
B. Because the portal to evil opens and evil comes out, the PC's forces are scattered and demoralized, but maybe not as much.
1.Some particularly martial and heroic PC's, if they are stationed with a unit, may be able to keep them from running (Paladin, warlord, war wizard?). Of course, if they're doing that, they're not with the rest of the party able to act as a squad of 16th level adventurers.
2.Forces in the safe zones are probably not scattered and demoralized.
3.PC's could use Insight checks to determine which units can keep it together without further supervision, then leg it with movement abilities or athletics checks to less brave units, who could be rallied with Diplomacy (good speech) Religion (prayers inspiring faith against evil) or History (Remember the face of your father!)
C.Fighting the evil entourage
DM fiat here: the evil entourage cannot be stopped by 6 characters, no matter how high a level. You can kill everything in reach and pile a breastwork of bodies around you, but surviving horde will just go past and around you. You need an army, or at least a squad of allies.
1.You can work to use your squad effectively:
Perception checks let you see an enemy squad with an exposed flank. Attacking that squad makes it easier for your side to win.
Athletics lets you lead your squad to favorable terrain before the enemy gets there. You get an advantage.
Stealth lets you lead an ambush.
Endurance lets you outrun enemies, helping you escape a tough encounter.
Religion lets you bless your troops, giving them some sort of limited combat bonus.
And when the squad goes into battle, you can enter combat and do a heroic deed to inspire them. Do, say, 30 points of damage in a round to give your troops some kind of combat bonus.
2.You can go find a squad that was scattered and get it back in the fight.
Healing skills and powers might help if they were damaged.
Rally them with Religion, History, or Diplomacy. Maybe Intimidation
3. If all your squads are gone, you can just try and dodge bad guys.
Use Stealth to hide
Use Athletics and endurance to outmaneuver the enemy.
Use Arcana and religion to ward yourself from their attacks.
Use Intimidate to scare them away.
D. Fighting the big bad
This could be easy. If the PC's have preserved their forces and hampered the big bad by corrupting his gate ritual and leading their forces well in battle, maybe you hand wave it.
"Trapped by his corrupted ritual, his entourage utterly destroyed, and facing the steely resolution of 10,000 noble warriors, the demon lord screams a curse and returns to the abyss."
If the entourage is not defeated, the PC's are facing a solo plus...lots of minions and a few real monsters. Maybe the entourage is only partly defeated, and its a solo plus lots of minions or a few real monsters
If the ritual is not corrupted, the PC's might be facing a full 16th level solo at full power.
If it was partially corrupted, the PC's might be facing a 16th level solo with a hampering condition...blinded, or restrained, or a 15th to 14th level solo.
If they totally messed it up for the big bad, maybe it's a 14th level solo with a hampering condition.
This is obviously really sketchy, vague, and fast.
I must also acknowledge at least 2 more issues: I didn't talk about designing or selecting a solo monster opponent, and I didn't talk about recruiting forces (another adventure in itself).
I hope you find it helpful, however.