Barca clinched the La Liga title on Sunday with a 1-0 win at Atletico, exactly a year after Simeone's side pipped them to the Spanish league trophy, their first in 18 years, with a 1-1 draw at the Nou Camp.
Atletico were able to capitalise on Barca and Real's inconsistency in 2013-14 but with one game remaining this term, are left fighting for third place and a berth in the Champions League group stage.
Atletico have 77 points in third, three ahead of fourth-placed Valencia, with Sevilla a point further adrift in fifth.
Simeone's men face a tricky final match on Saturday at Granada, who are 16th and fighting for the top-flight survival.
"We have to prepare as a team for when Real Madrid and Barcelona are not so attentive," Simeone told Spanish radio station Onda Cero in a late-night interview on Tuesday.
"Last year, they were not so focussed and we were able to get in the mix but Valencia and Sevilla are also aware of this and that strengthens the league," the Argentine added.
"To become champions again we have to work to finish second, third and when they (Real and Barca) get distracted win the title again."
Once Barca's prolific Argentina forward Lionel Messi, who scored the winner on Sunday, retired, Atletico would have an even better chance, he joked.
Simeone has long maintained that Atletico had little chance of defending their title given the gulf in resources compared to Real and Barca, insisting third place was a more realistic target.
Despite losing top scorer Diego Costa to Chelsea, Atletico have still put together an impressive season, twice beating Real in La Liga, including a 4-0 drubbing of their neighbours at the Calderon in February.
However, they lost both La Liga matches against Barca, were eliminated by the Catalan giants from the King's Cup and knocked out of the Champions League by Real in the quarter-finals.
"When we said that our rivals were Sevilla and Valencia we were right," Simeone said. "Until we know whether we have finished third we cannot give ourselves a mark for the season."
(Reporting by Iain Rogers; Editing by John O'Brien)
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