In electron cyclotron resonance (ECR) thrusters, the plasma mode transition is a critical phenomenon because it determines the maximum thrust performance. In ECR ion thrusters, ionization generally occurs in the magnetic confinement region, where electrons are continuously heated by ECR and confined by magnetic mirrors. However, as the flow rate increases, ionization is also observed outside the magnetic confinement region, and this induces the plasma mode transition. In our previous work, two-photon absorption laser-induced fluorescence (TALIF) analysis revealed that the stepwise ionization from the metastable state plays an important role in the ionization process. However, the distribution of the stepwise ionization has not yet been revealed because of the long lifetime of the metastable state. In this study, this distribution was investigated using one experimental and two numerical approaches. First, TALIF was applied to two types of gas injection with clear differences in thrust performance and ground-state neutral density distribution. In the first simulation, the metastable state particle simulation was used to estimate the excitation rate distribution. In the second study, simulations of the electric field of microwaves were used to estimate the contribution of the stepwise ionization to the plasma density. The experimental and numerical results revealed that the stepwise ionization spreads outside the magnetic confinement region because of the diffusion of metastable particles, and this spread induces the plasma mode transition, explaining the difference between the two types of gas injection.