We present a comprehensive relativistic quantum-mechanical theory for interaction of a free electron with a bound electron in a model, where the free electron is represented as a finite-size quantum electron wave packet (QEW) and the bound electron is modeled by a quantum two-level system (TLS). The analysis reveals the wave-particle duality nature of the QEW, delineating the point-particle-like and wavelike interaction regimes and manifesting the physical reality of the wave function dimensions when interacting with matter. This QEW size dependence may be used for interrogation and coherent control of superposition states in a TLS and for enhancement of cathodoluminescence and electron energy-loss spectroscopy in electron microscopy.