Research on new composite materials in the field of radiation shielding materials requires adequate means and meticulousness in their manufacture and characterization. In this study, concretes that use elements that theoretically improve their shielding properties are developed, such as fibers and boron-rich additions. Both magnetite and limestone concrete have been manufactured, incorporating steel fibers to improve the linear attenuation coefficient and polyvinyl alcohol to increase neutron scattering cross section. The incorporation of boron carbide is intended to increase the neutron absorption cross section. 5 mixes have been manufactured that have been tested with several gamma radiation sources (570–1280 keV) and with an Am–Be neutron source (111 GBq). The experimental results have been used to validate simulations carried out with MAVRIC® and have led to the modelling of a simplified spent nuclear fuel cask. Boron carbide produces a decrease of more than 50% on the neutron dose rate in contact with the cask. Incorporating PVA fibers supposes gain in neutron attenuation capacity of up to 13%, while fibers have a negligible effect on the photon dose rate.