Scimeca started his career at Aston Villa, coming through the club's youth system, as a central defender and was largely a squad player until his move to Nottingham Forest in 1999 for £2.5 million.
Nottingham Forest
He spent four seasons at the City Ground, and took over as captain when Steve Chettle left in his first season. However Chris Bart-Williams was appointed captain the following season. Scimeca was consistent and reliable in his spell at Forest, playing in various positions. He featured regularly in central defence and midfield, but also had spells at right back and right-midfield. He scored 4 goals in his second season. In the 2001–02 season he formed a solid defensive partnership with Jon Olav Hjelde. In 2002–03, his last season, in which Forest made the play-offs, Paul Hart deployed him in a defensive midfield role within a diamond 4–4–2 formation. He scored 4 goals during this season, and played a prominent role throughout his four years at the club.
He moved on to Leicester City in 2003, on a free transfer after failing to agree a new deal. At Leicester he scored once in a 4–3 defeat to Wolverhampton Wanderers on 25 October 2003. Scimeca then moved to West Bromwich Albion a year later by activating a get-out clause in his contract which allowed him to leave Leicester, before his transfer to Cardiff City in early 2006.
Cardiff City
In his first year at Ninian Park, Scimeca became an important part of the Cardiff side under manager Dave Jones and also developed something of a goal scoring touch which he admitted surprised him. At the beginning of the 2007–08 season he was sidelined with a groin injury and started the season on the treatment table. He attempted a comeback in August in a reserve match against Plymouth Argyle but only lasted twelve minutes after suffering a recurrence of the injury. He again came close to a return in December 2007 after having an operation on his groin injury but suffered another setback after he contracted the MRSA bacteria after the incision failed to fully heal. He made his long-awaited return for Cardiff on 19 February 2008, by playing for 45 minutes against Newport County in the FAW Premier Cup, his first appearance for the Bluebirds for nearly a year. He went on to make a total of 11 appearances in all competitions during the season, mostly as a substitute to return to match fitness. The start of the 2008–09 season looked to be more promising for Scimeca as he began the season fully fit and an injury to Gavin Rae saw him back into the first team early in the year, but he went on to suffer another injury setback after seriously damaging ankle ligaments during a 2–1 victory over Milton Keynes Dons in the second round of the Football League Cup. He returned to the squad for the first time on 22 November 2008 when he was named on the bench for a 2–1 defeat against Plymouth Argyle but did not make an appearance until the following week when he came on as a late substitute in the South Wales derby against Swansea City on 6 December. Despite his return, he made just two more appearances for the side during the rest of the season. In the 2009–10 season Scimeca made his 400th career appearance against his former club Aston Villa on 23 September 2009 in the League Cup. He returned to the starting line-up on 5 December in a 1–0 win over Preston North End and played in the following game against his former club West Bromwich Albion, where Cardiff won 2–0. After suffering a recurrence of a groin injury, Scimeca announced his retirement as a player on 17 December 2009.