This work presents a spectral color-imaging procedure for the detailed colorimetric study of real artworks under arbitrary illuminants. The results demonstrate this approach to be a powerful tool for art and heritage professionals when deciding which illumination to use in museums, or which conservation or restoration techniques best maintain the color appearance of the original piece under any illuminant. Spectral imaging technology overcomes the limitations of common area-based point-measurement devices such as spectrophotometers, allowing a local study either pixelwise or by selected areas. To our knowledge, this is the first study available that uses the proposed CIE (Commission Internationale de l’Éclairage) light-emitting diode (LED) illuminants in the context of art and heritage science, comparing them with the three main CIE illuminants A, D50, and D65. For this, the corresponding colors under D65 have been calculated using a chromatic adaptation transform analogous to the one in CIECAM02. For the sample studied, the CIE LED illuminants with the lowest average CIEDE2000 color differences from the standard CIE illuminants are LED-V1 for A and LED-V2 for D50 and D65, with 1.23, 1.07, and 1.57 units, respectively. The work studied is a Moorish epigraphic frieze of plasterwork with a tiled skirting from the Nasrid period (12th–15th centuries) exhibited in the Museum of the Alhambra (Granada, Spain).