As you said, CMYK is used in printing, and uses subtractive colors.
RGB uses additive colors and is used when emitting light directly.
RGB uses three different values for red, green blue, but they can be expressed either as float values between 0 and 1 each, or as integer values between 0 and 255. To make that standard and use that in web pages, we created the HEX system, which just takes the three values between 0 and 255 in hexadecimal (00 to FF) and concatenate them. This also has the advantage of being really short, which mattered quite a lot when modems weren’t as fast as they are today (think 3kb per second).
HLS is a format that is used by artists, because it’s easier for them to change a color by changing its hue, or saturation, or luminosity. If they want to go from a red to an orange, they just change the hue, as opposed to lowering the red value and increasing the green value together.
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