As a teenager, Madero was drawn initially to basketball, but decided on football when it became clear he had the talent to make it in the professional league. He played for Boca Juniors and Huracán but he came into his own with the Estudiantes de La Plata team that won several national and international titles between 1967 and 1970. He was also cited for the national team. He scored only nine goals forEstudiantes, but one of these goals was a crucial header against Quilmes that helped Estudiantes avoid relegation. Madero provided firmness but also elegance as a defender, playing alongside the less-polished Ramón Aguirre Suárez.
Madero and fellow player Carlos Bilardo retired after graduating as Medical Doctors. While Bilardo remained in football as a coach, Madero chose to specialize in sports medicine. In the late 1970s, he was team physician at Argentinos Juniors. When Diego Maradona transferred from Argentinos to Boca Juniors, Madero went with him and took part in the successful 1981 championship campaign. In 1983, newly minted national coach Bilardo asked his friend Madero to be the physician of the Argentina national football team. Madero accepted, and remained in the position until 1990. Argentina was champion of FIFA World Cup 1986 and finalist in the 1990 edition. The fitness trainer was another Estudiantes veteran, Ricardo Echevarría. After Bilardo's departure and a tenure as head of medicine with the Argentine Football Association, in 1996 Madero was made a member of FIFA's Sports Medical Committee and the FIFA Medical Assessment and Research Centre. In 2007, Madero was designated again as physician for the national team under coach Alfio Basile, who was Madero's teammate in the national team in the late sixties . Madero endorsed FIFA's decision to prohibit the playing of international matches at a height of 2500 m and above, citing medical concerns. In 2009, Maradona and Bilardo, now coach and manager of the national team, decided to reinstate Donato Villani as team physician, thus ending Madero's second term. Madero is also head of the Sports Medicine program in the Buenos Aires branch of the Pontifical Catholic University of Argentina .
