After playing his first two professional seasons at lowly Clube Caçadores das Taipas, Peixoto's ability as a left winger allowed him to jump from the fourth division straight into the Primeira Liga with C.F. Os Belenenses, thanks to former player João Cardoso. He would score seven goals in his debut season, one of them a long range shot closing a 3–0 win against FC Porto at the Estádio do Restelo. In July 2002 he signed with Porto, going on to be managed for two years by José Mourinho.
Porto
Peixoto's Porto career did not go as planned: while talented, he failed to impose in the first team, and in his first season only made 15 appearances, scoring three goals. Again with a slow start, he was starting to make his presence felt in the starting XI when, after netting in two consecutive league matches in 4–1 wins, he was seriously injured in the UEFA Champions League3–2 away victory against Olympique de Marseille on 22 October 2003 and, while it did not seem serious at first, on the next day a ruptured anterior cruciate ligament was diagnosed, which forced him to miss most of the season. After his recovery, Peixoto crashed his Mercedes-Benz SL500 while speeding to arrive in time at Porto's training center in Vila Nova de Gaia, and while only getting minor bruises, the car was completely wrecked and he was promptly asked for explanations by Mourinho. His image as a professional suffered much from the accident, and midway through the following campaign he was loaned to Vitória de Guimarães where he regained his previous form, returning to Porto for 2005–06. Facing another loan, Peixoto remained in the transfer list until the eleventh hour, being one of the final players to get a sit in the team. Following the internal problems with Nuno Valente and the sub par performances of Leandro, club manager Co Adriaanse turned him into a prolific left defender, in the same fashion of Portuguese internationals Miguel or Paulo Ferreira. After having scored twice at Associação Naval 1º de Maio in a 3–2 success – he also netted an own goal– Peixoto again suffered a major knee injury that would keep him away from the pitch for the rest of the season, eliminating any hope of World Cup selection. He would be dismissed by Adriaanse and joined La Liga side RCD Espanyolon loan for 2006–07, finally losing all ties with Porto in March 2007. Previously, on 27 February, Espanyol had also terminated Peixoto's contract, as the player failed to make any competitive appearances for the Catalans.
Braga / Benfica
On 30 May 2007, Peixoto signed a three-year contract with S.C. Braga. He declared himself delighted to join "...the fourth biggest club in Portugal." After two intermittent seasons, Peixoto refused to take part in Braga's 2009–10 UEFA Europa League fixtures against IF Elfsborg, after reported interest from S.L. Benfica, thus being suspended by the club. On 7 August 2009, a transfer deal between the two teams was arranged for a fee of €400,000 – however, Braga retained 50% of the player's rights. He spent most of his first season playing as left-back, battling for position with another adapted player, Fábio Coentrão. After appearing in 65 official games for Benfica, Peixoto was deemed surplus to requirements by manager Jorge Jesus as practically all Portuguese players, and was not given a jersey for the 2011–12 campaign, being ultimately released from contract on 6 January 2012.
Coaching
Peixoto finished his career with Gil Vicente F.C. in 2014, at the age of 34. He started working as a manager on 11 March 2019, being appointed at LigaPro side Varzim SC. On 19 June that year, after succeeding in avoiding relegation, he moved to Associação Académica de Coimbra in the same league; he left his post five months later, having collected only nine points in ten matches. On 19 December 2019, Peixoto signed with G.D. Chaves, succeeding José Mota at the team eighth in the second division.
In the 2005 off-season, photos of Peixoto and Portuguese model and presenter Isabel Figueira dancing and hugging appeared in the press, and after a few weeks both announced their engagement. The couple welcomed son Rodrigo on 2 September 2006. In October of the following year, they divorced.