At this early stage I usually try to have as few layers as possible. I like to jump all over the painting correcting any errors that I see when I see them. Having a ton of layers gets confusing and slows me down. I think for the image below I had one layer each for the background, the boy, the mermaid, and the water. Isolating each element allows me to move and adjust things quicker.
Next I added a blue layer and set the layer mode to multiply. This is like turning off the lights. It makes everything darker and unifies the shadow color. In traditional painting this would be like adding a transparent blue wash over everything.
The next step is to turn the lights on. This is done by setting the brush mode and the layer mode to linear dodge. Then paint in the lights with dark warm colors.
This is what the linear dodge layer looks like by itself. (The grid in the background is how Photoshop shows transparency) When this layer is added it lightens everything under it proportionally to how bright it is. For instance the darker green colors only lighten and tint slightly, while the bright yellow areas become almost pure white. Compare the previous two images to see the effect of this layer.
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