The development of erosion-resistant functional materials usable as plasma facing first wall components (PFC) is crucial for increasing the lifetime of future fusion reactors. Generally, PFCs have to be quality checked and characterized regarding their composition, before integrating them into the fusion reactor vessel. Enhanced X-ray fluorescence (XRF) methods represent an effective alternative to conventional analysis methods for the characterization of refractive metallic coatings on large areas of fusion materials. We have developed and applied XRF methods as fast and robust methods for the characterization of the thickness and composition uniformity of complex functional coatings. These coatings consist of tungsten included in multilayer configuration and deposited on low or high Z substrates. We have further developed customized calibration protocols for quantifying the element composition and layer thickness of each investigated sample. The calibration protocols are based on a combination of standard samples measurements, Monte Carlo simulations, and fundamental parameter theoretical calculations. The calibrated results are discussed considering a selection of relevant PFC samples. The deposition uniformity was successfully investigated for different PFC-relevant tiles and lamella shaped samples with W layers below and over the W L-line saturation thickness. Also, the 2D thickness mapping capability of the XRF method was demonstrated by studying the plasma post-erosion pattern.