Spanair serves Vigo, Santiago, Oviedo, Bilbao, Barcelona, Alicante, Malaga, Sevilla and Lisbon from Madrid along with Balearics and Canary Islands from Madrid. I don't know if you can use a SpainPass for Lisbon.
They don't do Burgos or Aranda de Duero in la Rioja) but you can get to either of those by bus or driving. They don't do Cordoba but you can get there from Sevilla on AVE or Talgo (1-hour).
For the 'wine tour' I would recommend Vigo (in Pontevedra, Galicia) and a wine called Albariño. Rosal is the finest of the wines of the Minho valley, if you can find it.
Across the border in Portugal you pass miles and miles of Viñas.
Bilbao has some excellent wines but Basque cuisine is what attracts me more to that region. You can take a bus Bilbao-Santander for some more interesting seafood specialties.
Barcelona has its 'Cavas,' sparkling wines like Champagne.
So, if I had a SpainPass and I wanted to drink some wine I would visit Vigo, Bilbao and Barcelona (and try to make a day or two in Portugal, either from Vigo to Porto or from Madrid to Lisbon).