Some more Classics. Romance ones.
Onegai Teacher (my favourite romance anime with a relation between a male student and female teacher)
Onegai Twins
Also Ano Natsu de Matteru (but it's from 2012 so not really a classic but it's similar to those above and worthy to watch)
and last is
Iriya no Sora, UFO no Natsu
thats all the series i have in my mind now
and then some classic romance movies
Tooi sekai (super short anime movie from Shinkai Makoto)
Hoshi no koe (more Shinkai Makoto and this is a really good short anime movie)
Kumo no Mukou, Yakusoku no Basho (from Shinkai Makoto and i don't know how many times i have held back my tears to this movie)