What I don't understand is how a freight car left standing can become a runaway, and how cars can be humped if the brakes are applied when they're not pressurized.
How train brakes work is widely misunderstood. Air does not directly keep the brakes released. Rather, a loss of air in the brake pipe causes pressurized air already in the reservoir on each car to flow from the reservoir to the brake cylinder.
The longer explanation is starting from a train completely empty of air in the brake pipe and the reservoirs on each car, the brake pipe first acts as an air supply charging the reservoir on each car to the brake pipe pressure. Once fully charged (takes a while, particularly for a long freight train), the train is ready to move. At that point, the brake pipe is acting primarily as a control signal. Reduce the brake pipe pressure 10 pounds and the reservoir on each car also reduces 10 pounds by sending that air to the brake cylinder (due to size difference, there's a 2.5 multiplier so a 10 pound brake pipe reduction puts 25 pounds in the cylinder). If the engineer then releases the brakes, the brake pipe starts charging back to the full pressure. As soon as the pressure starts rising, the control valve on each car vents the brake cylinder and the brakes release. Eventually, every thing comes back to full pressure and things are ready to repeat.
It takes time to fully recharge after brakes are released. Repeatedly apply and release and you eventually run out of air. That's why long freight trains rarely make running releases - once you take air, you stop and then wait for the brakes to fully recharge before moving again.
Also, you can't keep taking reductions. Once the air pressure in the reservoir on each car equals the brake cylinder pressure, that's all the braking you can get (except for emergency brakes). If you brake pipe pressure is 70 psi, a 20 pound reduction brings the brake pipe to 50, 20 pounds goes from the reservoir to the cylinder putting the reservoir at 50 psi as well, and the brake cylinder, thanks to the 2.5 multiplier, is also at 50 pounds. That's full service and that's all you can get.
Back to what I said about needing to wait to recharge, if I take a 20 pound reduction, release, and then immediately take another 20 pounds, because things never got significantly above 50, all I can get is 36 pounds in the cylinder (5/7 of 50 - the first application was 5/7 of 70 which is 50). My second application is not as effective as the first.
Leave cars standing without a locomotive and eventually all the air leaks away. That's why handbrakes need to be applied to standing cars.
FWIW, while I am not a licensed locomotive engineer, I am a qualified passenger conductor and interurban operator (same brake system) at the Illinois Railway Museum where I am fully qualified on air brake operation.