Near-field interactions between metallic surfaces and single molecules play an essential role in the application of metamaterials. To reveal the near-field around a photo-irradiated single molecule on the metallic surface, high-resolution photo-assisted scanning microscopy is required. In this study, we theoretically propose photoinduced force microscopy (PiFM) measurements of single molecules at the atomic resolution. For experimental demonstration, we performed a numerical calculation of PiFM images of various transition states, including optical forbidden transitions, and interpreted them in terms of the interaction between the molecular internal polarization structures and localized plasmon. We also clarified the critical role of atomic-scale structures on the tip surface for high-resolution PiFM measurements.