One of the most successful ways to model the multitude of electron and photon processes in plasmas is the approach used in collisional radiative (CR) codes. The accuracy of CR codes depends largely on the accuracy of the rates of each process. These rates are generally well approximated in hot, classical plasmas. However, in degenerate plasmas quantum effects can influence these rates and must be accounted for. Previous approaches have developed corrections to the classical rates using the free-electron-gas (FEG) approximation. Here, we use electronic structures beyond the FEG approximation and show how the collisional rates are affected by degeneracy in aluminum and iron plasmas. We find that the FEG is a good approximation for aluminum, whereas more complex electronic structures that include d orbitals, such as iron, deviate from the FEG approximation. This results in different degeneracy corrections to the collisional rates relative to those for the FEG. Although the general trend of the corrections to degenerate plasmas is captured by assuming an FEG, we show that more complex electronic structures can result in deviations, even outside the degenerate regime. This study further advances the treatment of free-electron quantum effects in collisional radiative models.