I honestly don´t know what the first anime aired in Spain was. I do know that one of the first ones that I watched was Area 88, in one of the local channels of my city.
After that, it was the usual. Sailor Moon, Dragon Ball Z, Mazinger Z... you know, the "oldies" mixed with some "newies". A couple years later we were getting things like Rurouni Kenshin (The Samurai Warrior here), Doraemon (we still get Doraemon every single damn day), Card Captor Sakura, Cowboy Bebop, Evangelion on public TV...
Currently, we are having One Piece, Naruto... mostly shounens which I absolutely hate, including reruns of Dragon Ball Z. Now I think about it, I believe our current situation is worse than when we got Evangelion, Bebop and CCS. These ones have actually disappeared in favour of reruns and Western cartoons that are total shit, like Winx.
My impression might be wrong, though, since I hardly watch TV anymore. (It was worth it to turn on the TV yesterday, though, since I got to watch the old, Western version of Sonic the Hedgehog, when Tails and him ate hotdogs).