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Red is 빨간색 or 홍색.
Green is 초록색 or 녹색.
Blue is 파란색 or 청색.
In each case, the first version is "pure Korean" while the second version comes from Chinese. Probably there are many other examples.
Is there a difference in usage, either in terms the actual color referred to or when one or the other is more appropriate?
Yes. They are interchangeable. But there is a slight difference of nuance - Sino-Korean tend to be considered a little bit more formal. Native Koreans use former ones much more, and latter ones are usually used in documents, not in dialogues.
P.S. 빨간색 is often interchangeable with not only 홍색, but also 적색. 홍색 is the red with relatively higher brightness and chroma.
