For me? The first anime related thing I saw as a kid was Spirited Away on VHS, I was awestruck from the animation and quality of the film.
For shows it would've been the usual Pokemon and DBZ. As I grew older I suppose my first proper anime show was watching streams of Neon Genesis Evangelion due to people talking about it at school.
I remember watching Totoro as a child not knowing it was an anime. Later I watched The Guyver (1989 OVA) on VHS at my cousin's. Evangelion and Lodoss War were the first fansubs I watched knowing they were Japanese.