Given a constant temperature, the pressure of the air in the tyre will only change if the volume changes.
As you put additional weight on the tyre, the tyre deforms, and inevitably the volume changes - but only very slightly. The shape of the tyre is only changing at the bottom, where the tyre is in contact with the road.
Say that the wheel is 26 inches diameter, then it has a circumference of 26x Pi inches = 81 inches approximately. The deformed part of the tyre is probably 3 or 4 inches of that at most, and maybe only an inch or two. Assume 4 inches.
4/81 = around 5%. That means that only around 5% of the tyre is deformed.
That part of the tyre that is deformed does not lose all of it’s volume. It might only lose, say 1/4 of its volume due to the change in shape.
So the total loss of volume is (on these very rough figures) 1/4 of 5% which is around 1.25%. That means that there will be a very slight change of pressure - something like 1.25%. On a pressure of 32 psi, that’s barely detectable.
So, how does it support your weight? because the pressure is acting equally on every square inch of the inside of the tube/tyre.
Making some more very rough assumptions:
The circumference of the tyre is around 81 inches.
The circumference of the tube at any given point is probably 4 inches.
Therefore you have a total of around 4 x 81 square inches.
4 x 81 = 324 square inches of inner tube, each resisting 32 psi of pressure.
324 x 32 is 10,368 = a lot of pounds. Similar principle to a hovercraft - a large amount of low pressure = a lot of lift. However, if the weight isn’t distributed evenly (put all the payload in one corner of the hovercraft; focus all the weight of the unicyclist on one small part of the tyre, where it touches the road) and it may “bottom out”.
Compressing air is fairly easy so when you sit on the uni, rather than it rigidly supporting you, the air moves about and finds a new equilibrium - a slight deformation of the tyre, and a very slight increase in pressure.