An intense terahertz field is applied to excite semiconductor quantum wells yielding strong non-equilibrium exciton distributions. Even though the relaxation channels involve a complicated quantum kinetics of Coulomb and phonon effects, distinct relaxation signatures of Coulomb scattering are identified within time-resolved photoluminescence by comparing the experiment with a reduced model that contains all relevant microscopic processes. The analysis uncovers a unique time scale for the Coulomb scattering directly from experiments and reveals the influence of phonon relaxation as well as radiative decay. © 2014 AIP Publishing LLC.