For a native spanish speaker, It's rather easy to differenciate the main accents and sometimes that can be enough to identify the country people come from. Accents: Porteño, Peninsular, Andino, Colombiano, Caribeño, Mexicano.
Inside every country, local people can identify what state / province / department they come from, but that's not possible for other countries. As a Colombian, I can Identify the main 10 colombian accents, but not the accents from Spain. All of them are equally "peninsular".
Inside my region (Andean Colombia) I can Identify some nuances that allow me guess more precisely the place, but I'm not capable to do the same with other regions. For instance, I can Identify that someone is from the Caribbean region, but not what city exactly and sometimes not even if this caribbean person is from another caribbean country. But Caribbean People can stablish if Someone is from Cartagena or Guajira.
I live in a big city (Bogotá, 8 Million) and I can identify the zone bogotanian people come from and even the social status (sort of).