How to add custom colors into the color swatches for variants/options on the product page

When I add a single color name like red, green it works fine but when the color name is like dark grey, indigo blue it's not showing up any color?

You need to create custom colors from theme settings.
If you want to define the Dark grey color, please navigate to Customize > Product Pages > Sections > Product Page
Scroll to the bottom and add a color title with Dark grey and pick color or image.

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