What is the ambient color of the scene? (sorta like global reflected light.). Is there any reflected light (radiosity) that hits the surface?. Try to figure out if there are any shadows that might be falling on the surface. Well, actually you shouldn't have to think about them, it should just go automatically. You must consider many things while painting: Layers, Exposure/Lighting, Shadows, Highlights, Surfaces, Materials, Textures, Translucency, Reflections, Composition, and Color Temperatures Article by Arne Niklas Jansson The onion (Thinking in layers)īefore laying down a stroke, there's a number of things you need to think about. 
If you are completely new to Photoshop, you may want to go through these lessons, they provide a fantastic starting point for beginners: Photoshop Guide
Digital Painting & Concept Art with Photoshop Basic to Advanced Color Theory and Illustration Techniques for Photoshop
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