The properties of time-dependent cylindrical and spherical, modified ion-acoustic (mIA) solitary structures in relativistic degenerate multi-ion plasmas (containing degenerate electron fluids, inertial positively-, as well as negatively-, charged light ions, and positively-charged static heavy ions) have been investigated theoretically. This investigation is valid for both non-relativistic and ultra-relativistic limits. The well-known reductive perturbation method has been used to derive the Korteweg-de Vries (K-dV) and the mK-dV equations for studying the basic features of solitary waves. The fundamental characteristics of mIA solitary waves are found to be significantly modified by the effects of the degenerate pressures of the electron and the ion fluids, their number densities, and the various charge states of heavy ions. The relevance of our results in astrophysical compact objects like white dwarfs and neutron stars, which are of scientific interest, is briefly discussed.