Multi-Quantum well solar cells (MQWSC) have been shown to present several advantages, among which are low dark currents and tunable bandgaps. They are especially suited for implementation in multi-junction cells, and are highly promising for absorbers in Hot Carrier Solar Cells (HCSC). Such applications require high concentration ratio, which arises the issue of collection efficiency. Whereas it is usually considered that collection in MQW is very close to unity at one sun, it has been shown to not be the case under high concentration at the maximum power point. We propose in this work to take advantage of the luminescence spectral variation to investigate the depth collection efficiency. In order to validate the model, a series of strain compensated InGaAs/GaAsP MQW solar cells with intentional variation of the MQW doping concentration are grown. This has the effect of switching the space charge region position and width as well as the electric field intensity. Recording the luminescence spectra at various illumination intensities and applied voltages, we show that the in-depth quasi-Fermi level splitting and thus collection properties can be probed. Other measurements (EQE, luminescence intensity variation) are shown to be consistent with these results. Regarding their use as HCSC, the luminescence of MQW solar cells has been mainly used so far for investigating the quasi-Fermi level splitting and the temperature. Our results improve our understanding by adding information on carrier transport.