PSI stands for Pounds per Square Inch. It's the amount of force per square inch of volume that air is exerting. 4500 PSI means that there's an additional 1500 Pound per Square Inch throughout the volume of the tank from a 3000 PSI. Tank volume is measured in liters in Europe and Cubic Inches (CI) in the states. Volume is the amount of space in which air is compressed to it's desired pressure (3000, 4500 and 5000 PSI are the only three tank pressure's in paintball that I'm aware of). So, for example, in a 68 CI 4500 PSI tank, there are 4500 Pounds per Square Inch of pressure throughout 68 Cubic Inches of space.
Obviously markers don't run on 4500 PSI, so every tank is equipped with a regulator (abreviated "reg") to take that pressure down to one usable by your marker. Preset regulators are non-adjustable regulators (since the output pressure for the tank is pre-set at the factory, and the reg is non-adjustable, they are called Preset/Pre-set regs) that usually screw into a standard Air Source Adapter (ASA) (because of their ability to screw into an ASA, Preset regs are often called "screw-in" regs. Also, ASA's are sometimes referred to as a "Bottomline" because they mount to the bottom of your gripframe and have an air line attached to get air to your marker). They usually come with either a Low Pressure (LP) reg or High Pressure (HP) reg. A Low Pressure reg has an output pressure usually of 450-500 PSI. A High Pressure reg has an output pressure of usually 800-850 PSI. A popular example of a Preset reg is the Crossfire LP and HP. You can also buy adjustable regulators, which allow you to manually set the output pressure so that you can optimally match it to your marker. Adjustable regulators usually do not screw into a standard Air Source Adapter, but use their own mounting system to attach to the bottom of the grip frame of your marker, and have an air hose directly attached to the regulator. Some popular examples of an adjustable reg would be the Evil Scion, Angel AIR, Smart Parts Max Flo, or Air America Armageddon.
Hope that takes some of the mystery out of High Pressure Air (HPA) systems for ya.