Born in Corroios, Seixal, Setúbal, Simões joined S.L. Benfica when he was 15, and was already an important first-team member just two years later, being part of the squads that won ten national championships and one European Cup. In the 1962 final of the latter competition, a 5–3 win against Real Madrid, he became the youngest ever player to conquer the tournament, at 18 years and four months.