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I think one of the most famous cases is represented by Arsenio Erico. Born in Paraguay in 1915, he moved to Argentina when he was very young. He is the all-time highest goalscorer in the Argentine first division, with 295 goals. Alfredo Di Stéfano used to define him “the best player I've ever admired”. In spite of all, he never represented the two National teams.
For Scotland - I don't know whether Neil agrees - I would mention the striker John Campbell. He was the top-scorer in the English League three times.
For Italy, well, there's a long and interesting list. I just cite two champions: goalkeeper Sebastiano Rossi and stopper Sergio Brio. Rossi was one of the best Italian goalkeepers in the 1990s. He won a Champions League with AC Milan and still holds the record for the longest streak without conceding a goal in Serie A history. He was called up in just two occasions, but never played for Italy.
Brio was a formidable marker in the 1980s. If I just think that Andrea Ranocchia owns 18 caps and Sergio Brio none, I go mad!!! Jokes apart, Sergio also won as protagonist all the international competitions with Juventus and neutralized almost all the best strikers of that time.
In your countries, which are the best players who never got the chance to appear for the National team?