The first time I ever “shipped” two fictional characters was when I watched Prince Lotor try to get Princess Alura in Voltron. The next time I remember shipping another non-canon couple was when I watched Xena and wished she would hook up with Ares, the god of war (which turns out to be slightly incestuous since this Wikipedia article says that it was implied he might be her father, not her lover).
Anyway, Xena was the first badass chick I’ve ever admired. Sailor Jupiter (Sailormoon), Linka and Gi (Captain Planet), Storm of Xmen were some other female heroes I liked, but for me they were sissies compared to Xena. The woman was a female war machine, and, as amazing as I think those other ladies were, I doubt they could beat Xena in combat without the aid of any of their powers.