That result gave Atletico a welcome boost after a damaging 3-0 loss to Real Madrid at Vicente Calderon – a second straight league defeat which left them nine points behind their city rivals at the top of the table in sixth place.
But, speaking ahead of Sunday's away match against Osasuna, Simeone stressed domestic duties will always be Atletico's top priority – even if they are faring better in other tournaments.
"Since arriving here we have always approached every competition with the same enthusiasm," Simeone told reporters.
"The Copa del Rey has traditionally been an important competition in the history of our club. The Champions League is stimulating and up until now we had not qualified for the last 16 so regularly.
"I've always said, though, that the league means everything to me. At all the clubs I have been at the league is the most important thing for both the fans and the club.
"The league table is published on Sunday and every other day of the week in newspapers and fans can see if their team are fifth, fourth, tenth or second in the table. It means a lot to the fans.
"There is the Copa del Rey and the Champions League and also the league, which has games week in, week out."
Simeone hopes the win over PSV will have his team in the right mind-set for their trip to struggling Osasuna, who sit second from bottom.
"To win again and in the manner in which we did is positive for the team and bodes well ahead of our next match," added the coach.
"We are going to face a team which needs to pick up a good result. They are managed by a coach I have a lot of respect for.
"He always transmits positive energy to his teams. That energy will enhance the atmosphere surrounding the game. We have to be prepared for a high-tempo game.
"They will probably look to play to their target man [Oriol] Riera who is good in the air. We will try to play the game in a way that suits us best."