Spin orientation of photoexcited carriers and their energy relaxation is investigated in bulk Ge by studying spin-polarized recombination across the direct band gap. The control over parameters such as doping and lattice temperature is shown to yield high polarization degree, namely larger than 40%, as well as a fine-tuning of the angular momentum of the emitted light with a complete reversal between right- and left-handed circular polarization. By combining the measurement of the optical polarization state of band-edge luminescence and Monte Carlo simulations of carrier dynamics, we show that these very rich and complex phenomena are the result of the electron thermalization and cooling in the multi-valley conduction band of Ge. The circular polarization of the direct-gap radiative recombination is indeed affected by energy relaxation of hot electrons via the X valleys and the Coulomb interaction with extrinsic carriers. Finally, thermal activation of unpolarized L valley electrons accounts for the luminescence depolarization in the high temperature regime.