Inelastic X-ray scattering (IXS) spectroscopy has been used in many fields of solid-state physics and theoretical chemistry as an accurate and quantitative probe of elementary excitations. We show that non-resonant IXS spectra in the energy loss range below 100 eV exhibit a strong contrast across a wide range of commercially available pigments, opening new routes for their discrimination. These signatures combine plasmonic transitions, collective excitations and low energy absorption edges. We have performed IXS to discriminate different artists' pigments within complex mixtures and to quantitatively determine rutile and anatase polymorphs of TiO2. The integration of experimental data on pigment powders with suitable ab initio simulations shows a precise fit of the spectroscopic data both in the position of the resonances and in their relative intensity.