It can be possible by XPS and for other techniques you may do UV-vis analysis. There you can anlyse from the electronic transition occurs between Sn2+ and Sn 4+. Anyway, its better to do XPS analysis and I'm sure you can distinguished these states.
Please draw the particular spectra of Sn. Deconvolution the curve. The B.E. for Sn2+ and Sn4+ is very close. Draw the spectra within 450-500 eV. You will get spectra aroung 285-286 eV and for Sn4+ it will be at 486.4 or 486.6 eV. Your figure shows the survey spectra i.e. the whole spectra.
Thanks P. Boolchand, I found Mossbauer spectroscopy should be the most sensitive way to monitor the Sn2+/Sn4+ ratio, especially when one kind ion is dominated in the composition.