Best there is to offer are the radio feeds, like Radio Marca, Cadena Cope, Catradio, Radio Galicia, and the Radio Sur (or something like that). Most Real Madrid matches are on Radio Marca.
It´s Semi-Live and only the top teams get the coverage. About 10-15 minutes after each play. But it´s good enough if you can´t catch your La Liga team on the tube... Good Job ESPN!
Both Marca (www.marca.es)and AS (www.as.com) do minute by minute play by play for most first division matches. Well, not necessarily minute by minute, but they update with scores and significant plays at least every 5-10. As with the radio feeds mentioned above, these are all in Spanish. As far as English goes, I doubt you'll get a whole lot of play-by-play coverage, other than the ESPN site mentioned above.