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Probably a dumb question here, but I am going to ask it anyway. Does anyone know of what colors should be shaded with which Citadel Shade? I have color schemes in mind, but not totally sure of which shade to use when. Any help would be greatly appreciated. I have also provided a list of all the shades currently available.

Seraphim Sepia
Druchii Violet
Nuln Oil
Carroburg Crimson
Coelia Greenshade
Agrax Earthshade
Reikland Fleshshade
Drakenhof Nightshade
Athonian Camoshade
BIel-Tan Green
Casandora Yellow

It's impossible to answer this question, because any color can be shaded with any shade depending on what effect you want. As a general rule you normally shade with a color that is close to the base color, but you might use black or brown to shade the entire model at once.

^^ Exactly.

One thing to note on the side, just saying, but Army Painter do a shade system as well, Quickshades, but it only consists of light tone, mid tone and dark tone. They probably do more, but this tells you a lot about general shading, in real terms going and getting the full range is OK but probably unnecessary depending on the level of painting you wish to do. So Sepia, Eathshade, and Nuln Oil will get you most of the way, with a fleshtone, if you are doing a lot of human skin. Couple years ago everything was bathed in Devlan Mud (Agrax Earthshade-ish) It is all a matter of taste and how far you want to go with the painting.