The resistance switching phenomenon in many transition metal oxides is described by ion motion leading to the formation of oxygen-deficient, highly electron-doped filaments. In this paper, the interface and subinterface region of electroformed and switched metal-insulator-metal structures fabricated from a thin Fe-doped SrTiO3 (STO) film on n-conducting Nb-doped SrTiO3 crystals are investigated by photoemission electron microscopy, transmission electron microscopy, and hard X-ray photoelectron spectroscopy in order to gain a deeper understanding of cation movement in this specific system. During electroforming, the segregation of Sr to the top interface and the generation of defect-rich cones in the film are observed, apparently growing from the anode toward the cathode during electroforming. An unusual binding energy component of the Sr 3d emission line is observed which can be assigned to Sr-n"-VO** defect complexes by performing ab initio calculations. Since this Sr component can be reversibly affected by an external electrical bias, the movement of both oxygen and Sr point defects and the formation of defect complexes Sr-n"-VO** during resistive switching are suggested. These findings are discussed with regard to the point defect structure of the film and the local oxidation of the donor-doped substrate. In particular, the apparent dichotomy between the observation of acceptor-type defects and increased electronic conductivity in STO is addressed.