The Wikipedia article is pretty vague though.
For starers, when you move at very high speeds, you create shockwaves, which cause enormous jumps in pressure, temperature and density over a short distance that get even larger with high speed.
For example, across a normal shock at Mach 25, the temperature downstream of the shock will be almost 125 times higher than upstream of the shock! The ambient temperature at, say, 120,000 feet, is about -26°F, or 241 K. That means that the temperature behind the shock is 29,515 K or 52,668°F! That is over 5 times the temperature of the surface of the sun! Now, here the ideal gas law doesn't apply and you have to take into account chemistry and ionization, but the concept still holds.
Of course, the space shuttle quickly passes through these kinds of temperature regimes since it is moving so fast. Once you get down to Mach 10 or so, which is still quite fast, the temperature increase across the shock "only" increases by a factor of 20. Of course that is still 4820 K, or just slightly less than the surface of the sun at the free-stream temperature mentioned before. This is one reason it is so important to decelerate quickly and therefore why they design re-entry vehicles to have very high drag.
So that explains the most notable way the temperature increases. The rest is just convection. It is the opposite of how you blow on your coffee to help it cool faster. Instead, the air flow tends to try and bring the vehicle into thermal equilibrium with itself, so it gets really hot, really fast. Even Fourier's law of heat conduction would predict extraordinarily high heat transfer rates with a temperature difference like that, but factor in convection and radiation and it gets worse. That is why we need exotic heat shields.