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Can I use Immaculately Groomed for male or female?
If not what is the corresponding words for the male?
"Grooming" in the context refers to how one carefully styles the hair or wears smart clothes. It can apply to both men and women, and is perhaps even more common for men than for women.
I wouldn't use this phrase for either a male or a female, perhaps a dog or a cat?
Instead, when males look good, we'd say they are "handsome", for females they look "beautiful".
Yes, you can use it for both – though ordinarily you shouldn't capitalize it, as you've done in your question. If you want to be fancy (some would day pretentious), another option would be to use "soigné" for a man and "soignée" for a woman.