XPS is sensitive towards the chemical surrounding of the affected atoms, so the answer is yes. However, it's not fully straightforward, you will require some components:
1) A reference sample with a defined binding energy for the dopant atom
2) Your actual measurement with a sufficiently high resolution
3) Quantum Chemical calculations on the same level of theory for the reference system and all dopant position candidates.
By comparing the measured shift to the calculated shifts, you can narrow down the potential positions, or, in the best case, lock in on one.
If you ask about an energy level related to dopand in the bandgap of semiconductor, the energy level of aceptor can be tested by Valence Band Analysis.