It's a matter of ability. When a fan blade moves through air, it creates a vacuum behind it, the byproduct of that movement is the exhaust movement of air. The faster the blade moves, the more draw is created. Vacuum draw doesn't reach very far effectively, but is good only for a short distance. Nature abhors a vacuum, so whatever air is easiest and closest will fill it, hopefully including a bunch of heat. This requires air to fill that void. This is where intakes come in, supplying cooler air to replace the warm air vacating through the exhausts.
In a pc, there's 2 sources of cooler air. What the intakes provide and every gap, seam, vent, crack, hole available. In what ppl erroneously call a negative pressure system, there is more vacuum created than intake exhaust can supply. So the exhaust fan vaccum will take air from wherever it can, usually gaps around the fan, top exhaust vents, pcie slots by the gpu. With an aio mounted at rear exhaust, this makes for slightly cooler cpu temps as the immediate air is not heated by gpu/motherboard/case heat, but is direct from the outside, making the radiator more efficient. Case temps will be higher not lower, due to minimal actual airflow allowing case heat to accumulate.
Nothing to do with the amount of fans. Exhaust fans invariably run faster than intakes. The ISA buss sensors controlling the exhaust will be on a warmer area than the sensors for the front fans, so duty cycle is raised. It's very easy to have a single exhaust at higher cfm than 2x intakes, or vice versa.
In a positive pressure system, there's more intake cfm than exhaust, so this will flood the aio rad. Since this air is also picking up gpu/mobo/case heat, it'll make the radiator less efficient, raising cpu temps 1-2°C but overall case temps will be cooler by 1-2°C, as will gpu, drives, VRM's etc.
And the kicker is that this all changes depending on the fans and rpm and ability curves. At low rpm (idle) its very easy to have a negative system that upon raising duty cycle turns to positive or the other way around.
There's a whole lot more that goes into case airflow and thermal dynamics than just having a slightly lower cpu temp.