Born in Portonovo, Pontevedra, Rico joined local Pontevedra CF's youth ranks at the age of 14, making his senior debut on 18 December 2005 in a Segunda División B match against CD San Isidro.
Mainly a substitute in his first year, he became an important part of the Galicians' squad in the following seasons.
In the 2008 summer, Rico joined Real Madrid, being assigned to the reserve team also in the third division. He made his debut on 31 August, scoring the first goal in a 2–0 win at UD Vecindario. On 14 September, in only his third appearance, against CD Alfaro, he suffered an anterior cruciate ligament injury only eight minutes after the start of the match, being lost for the rest of the campaign.
Thirteen months after his injury, Rico played his first game of the season, against RSD Alcalá. On 8 November 2009, less than one month later, he scored twice against Gimnástica de Torrelavega in a 4–2 home victory.
In the first round of 2010–11, Rico found the net against Coruxo FC in a 3–2 home win. He scored a career-best six goals during the campaign, including one in the unsuccessful promotion playoffs.
On 5 August 2011, Rico left Castilla and signed for Granada CF, with Real Madrid retaining an option for the player in case of a future transfer. On 25 September, he scored his first La Liga goal in only his second league game for his new club: after replacing Moisés Hurtado at half-time, he netted the equalizer in an eventual 1–1 home draw against CA Osasuna.
In April 2012, Rico was sidelined for the rest of the season after suffering another injury to his right knee. He also missed the entirety of the following campaign.
Rico was an ever-present figure for the Andalusians in 2013–14, with his side narrowly avoiding relegation. On 26 February 2015 he renewed his contract with the club, until 2020.
On 26 August 2016, Rico was loaned to fellow top tier side SD Eibar for two years.As of 23 January 2016