X-ray fluorescence (XRF) spectrometry has proven to be a core, non-destructive, analytical technique in cultural heritage studies mainly because of its non-invasive character and ability to rapidly reveal the elemental composition of the analyzed artifacts. Being able to penetrate deeper into matter than the visible light, X-rays allow further analysis that may eventually lead to the extraction of information that pertains to the substrate(s) of an artifact. The recently developed scanning macroscopic X-ray fluorescence method (MA-XRF) allows for the extraction of elemental distribution images. The present work aimed at comparing two different analysis methods for interpreting the large number of XRF spectra collected in the framework of MA-XRF analysis. The measured spectra were analyzed in two ways: a merely spectroscopic approach and an exploratory data analysis approach. The potentialities of the applied methods are showcased on a notable 18th-century Greek religious panel painting. The spectroscopic approach separately analyses each one of the measured spectra and leads to the construction of single-element spatial distribution images (element maps). The statistical data analysis approach leads to the grouping of all spectra into distinct clusters with common features, while afterward dimensionality reduction algorithms help reduce thousands of channels of XRF spectra in an easily perceived dataset of two-dimensional images. The two analytical approaches allow extracting detailed information about the pigments used and paint layer stratigraphy (i.e., painting technique) as well as restoration interventions/state of preservation.