It's supposedly simple. You should be able to make a new scenario file (.eug), by copying an existing one, and editing it to exchange the country you want for one of the existing countries.
I haven't actually done this, yet, but looking at the alternate GC scenario that includes a Dutch nation, it looks like they just copied the GC .eug file, replaced the Austrian Hapsburgs (HAB) with the Netherlands (HOL), and assigned appropriate parameters. But, of course, the other seemingly simple aspects of this game are needlessly muddled, so this might be a bit more challenging than it looks.
Still, like the game itself, it'll probably be worth the effort. I think I read somewhere, though, that you will get very few colonists, as a minor.
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