Sources of indigo pigment
In medieval Europe, indigo was prepared as a pigment by skimming and drying the flower from the surface of a woad vat, called blue florie, or grinding white lead with imported indigo. Indigo was widely available, fairly inexpensive, and in common use as a workaday blue pigment. It is a strongly tinting, dark, and slightly greenish shade of blue. Indigo is certainly a regal dye, one of the few lightfast historical grand teints. But as a pigment, its lightfastness did not match the more permanent and expensive mineral blues.
For use as a pigment today, pure indigo can be finely ground and mixed as watercolor, tempera, or oil paint. If you're a dyer, you can use the botanical indigo powder you already have on hand. You can also purchase the genuine botanical pigment from Kremer,* from Cornellisen in the UK, or you can buy Genuine Indigo paint pre-made by a reputable paint manufacturer.
Synthetic indigo was formulated in the late nineteenth century and is chemically identical to indigotin. Slight color variations between synthetic and botanical indigo are due to additional organic compounds extracted from different species of indigo bearing plants, including the colorant indirubin, which influence the shade of blue. Either botanical or synthetic indigo can be used as a pigment, but not indigo dye sold 'pre-reduced.'
*or get sidelined by Tyrian purple, the other famous vat dye with similar chemistry