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the basic color wheel used to confuse me because i tend to like really desaturated colors. if you're like me you can try taking the color wheel into photoshop and desaturating it then lightening and darkening it to find your base colors. 
i then mess with making one color more saturated than the others if i want saturation to be my contrast. (the browns and reds in the sirens pieces are higher saturation than the blues)
re: saturation: it is so hard to gauge. especially when you're first starting out. things tend to be less saturated than I initially perceive them to be. so as a general rule I make one or 2 colors saturated, and the rest I bump down.
if you want to practice determining relative saturation, take a bunch of photos with different lighting/color palettes and do exactly what i did here. paint little dots of what you think the main colors are, and then color pick the photo to find the true color.
a couple people in my mentions are confused about the difference between the opacity and saturation sliders. lowering the opacity affects both the saturation and the value. lowering just saturation maintains the value (fairly closely)
for clarity
