We study the electron dynamics at a monocrystalline Pd(111) surface with stepped vicinal nanostructures modeled in a simple Kronig-Penney scheme. The unoccupied bands of the surface are resonantly excited via the resonant charge transfer (RCT) interaction of the surface with a hydrogen anion reflected at grazing angles. The interaction dynamics is simulated numerically in a quantum mechanical wave packet propagation approach. Visualization of the wave packet density shows that, when the electron is transferred to the metal, the surface and image subband states are the most likely locations of the electron as it evolves through the superlattice. The survival probability of the interacting ion exhibits strong modulations as a function of the vicinal-terrace size and shows peaks at those energies that access the image state subband dispersions. A simple square well model producing standing waves between the steps on the surface suggests the application of such ion-scattering at shallow angles to map electronic substructures in vicinal surfaces. The work also serves as the first proof-of-principle in the utility of our computational method to address, via RCT, surfaces with nanometric patterns.