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Transmission-based imaging and X-ray diffraction-based material analysis have largely developed independently. However, for a variety of applications ranging from in-vivo soft tissue analysis to concealed explosives detection, it is necessary to realize high-fidelity, spatially-resolved material discrimination. We therefore seek to understand to what degree transmission and X-ray diffraction (XRD) complement one another and can be implemented practically, particularly in the case of explosives detection in aviation security. Using a combination of simulated and experimental data, we identify the relative value of the X-ray signatures available to transmission and XRD measurements, and explore how the measurement fidelity can impact these results.