An X-ray macroprobe spectrometer is used to analyse small pigment samples and to determine the elemental composition of layered pigment specimens from works of art. The cross-section technique has been improved upon considerably since the first results were published in 1969 and a better understanding of the capabilities and limitations achieved. The improved macroprobe cross-section technique is described and evaluated using the results from studies of the 17th century painting, an 18th century polychrome sculpture as well as from an 18th century gilded altar. A short discussion of basic macroprobe theory is also included.