Periodically driven quantum systems, known as Floquet systems, have been a focus of non-equilibrium physics in recent years, thanks to their rich dynamics. Not only time-periodic systems exhibit symmetries similar to those in spatially periodic systems, but they also display novel behavior due to symmetry breaking. Characterizing such dynamical symmetries is crucial, but the task is often challenging, due to limited driving strength and the lack of an experimentally accessible characterization protocol. Here, we show how to characterize dynamical symmetries including parity, rotation, and particle-hole symmetry by observing the symmetry-induced selection rules between Floquet states. Specifically, we exploit modulated quantum driving to reach the strong light-matter coupling regime and we introduce a protocol to experimentally extract the transition elements between Floquet states from the coherent evolution of the system. Using the nitrogen-vacancy center in diamond as an experimental testbed, we apply our methods to observe symmetry-protected dark states and dark bands, and the coherent destruction of tunneling effect. Our work shows how to exploit the quantum control toolkit to study dynamical symmetries that can arise in topological phases of strongly-driven Floquet systems.