Quasi-particles formed in lithium niobate after pulse exposure were investigated by transient absorption and photoluminescence spectroscopy as well as numerical simulations. This includes the formation process, the transport through the crystal, interim pinning on defects during the relaxation process, and the final recombination with deep centers. It was shown that the charge-transport through the crystal can be described by a hopping transport including different types of hops between regular or defective lattice sites, i.e., the transport includes a mixture of free and bound small polarons. Furthermore, the different types of hops connected with varying activation energies and their distribution are responsible for an altered temporal decay curve when changing the crystal composition or temperature. Additionally, it was shown that the hitherto accepted recombination model is insufficient to describe all transient absorption and luminescence effects in lithium niobate under certain experimental conditions, i.e., long-living absorption dynamics in the blue/UV spectral range do not follow the typical polaron dynamics and cannot be described under the assumption of charge compensation. However, similar decay characteristics between self-trapped excitons known from photoluminescence spectroscopy and the unexpected behavior of the transient absorption were found leading to a revised model. This includes, besides the known polaron relaxation and recombination branch, a significant role of self-trapped excitons and their pinning on defects (pinned STEs). Since the consideration of further absorption centers in the relaxation path after pulse exposure might result in misinterpretations of previously determined polaron absorption cross-sections and shapes, the necessity to perform a review became apparent. Therefore, a supercontinuum pump-probe experiment was designed and all measurements applied under the same experimental conditions (temperature, polarization) so that one can extract the absorption amplitudes of the single quasi-particles in a spectral range of 0.7-3.0eV. The detailed knowledge might be used to deconvolve the absorption spectra and transform them to number densities of the involved centers which enables one to obtain an easier insight into recombination and decay dynamics of small polarons and self-trapped excitons. As the hopping transport of quasi-particles and the concept of pinned STEs might be fundamental processes, a thorough understanding opens up the possibility of their exploitation in various materials. In particular, results presented herein are not only limited to lithium niobate and its applications; an extension to a wide range of further strongly polar crystals in both their microscopic processes and their use in industry can be considered.