If your flight leaves Spain, EU passenger rules apply whoever paints the tail. Madrid, Barcelona, Málaga, Palma, Alicante, Valencia: the airport is in the European Union, so a delay of three hours or more at arrival, a short-notice cancellation, or involuntary denied boarding can be worth €250, €400, or €600 per person. Iberia, Vueling, Ryanair, easyJet, and a US carrier departing Madrid are under the same test. This page does not score those airlines.
Leaving Spain, or flying into it
Departures from Spanish airports are covered. Arrivals into Spain are covered when the operating airline is an EU carrier. A non-EU airline flying you from Latin America to Madrid is not an EU261 departure. The return, Madrid to Bogotá on that same airline, is, because it leaves Spain.
The bands, from EC 261/2004: €250 up to 1,500 km, €400 from 1,500 to 3,500 km and for longer flights inside the EU, €600 beyond 3,500 km. A long-haul figure can be halved if you arrive under four hours late. Notice of a cancellation 14 days ahead usually removes the fixed sum. You still get a refund or a new flight.
Weather and air-traffic restrictions are the common refusals. "Operational reasons" on a text is not, by itself, a legal answer. Care, meals and a hotel when you are stuck, is separate and can be owed even when compensation is not.
A note on the carrier
Claim against the operating airline, the one whose crew flew the sector, unless your contract says otherwise. A codeshare sold by one brand and flown by another is a frequent mess at Madrid. The boarding pass is the better document than the confirmation email. The same point, for a German hub, is in the Germany guide published alongside this one.
Does Vueling pay a different amount from Iberia?
No. The regulation sets the amount. The airline does not.