I suggest you to select the appropriate excitation wavelengths from the UV-Visible spectrum ( wavelength range which shows one-set increase in the absorbance ) and analyze the corresponding PL spectra to find out the best and accurate result.
You need to identify if the two transitions are obeys the direct or indirect absorption, that was not obeyed, then you may have one of the transitions be due to defects and the other due to the bund transition