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Windows boarders can be changed, visit your Windows settings under personalization, and colours.
If you mean like the Steam skin UI, then that something else, can be done by editing the Steam files, or even getting pre set made Steam skins like Metro skin, or etc... For Library that can be done by editing the steam .css files in notepad, just need to find the colour for whatever part you want to change colours for.
Emphasis added on the part you missed.
Heres the solution for anyone that doesnt have the title bar option