It’s that you’re sticking the entire volume of brake fluid that will soon be in the car into a vessel, and then stuffing in air. Anyone who’s ever opened the petcock on a charged air compressor knows that water gets squeezed out of the air when you compress it, because when you open the petcock the first thing that shoots out the drain is a whole bunch of water.
That tells you three things: Air is wet, compressed air sheds water, and that water drops to the bottom of the vessel.
So if you put brake fluid in a vessel and then stuff in compressed air on top of it, that water is going to precipitate out of the air and head straight for the brake fluid, and you are now exposing all of the brake fluid to the water, not just the small surface area that you find on top of a MC reservoir.
Worse yet, if you vacuum bleed or do the old standard brake pump bleed, you’re exposing the top of the brake fluid in the MC to the water that is in the air directly above the master cylinder, which isn’t all that much even if you live in a very humid area.
If you pressure bleed in a non-separated vessel, you are exposing all of the brake fluid to the water that is normally in a vastly larger volume of air, because that’s what air compression is - you’re taking a big volume of air and stuffing it into the space normally occupied by a small volume of air.
You therefore have lots more water interacting with the brake fluid than you do with normal air.