Atletico, the 2014 runners-up, dismissed Turkish club Galatasaray 2-0 at the Calderon thanks to an Antoine Griezmann double and are level at the top of Group C with Portuguese side Benfica heading into the final matchday.
They each have 10 points from five games, with Atletico ahead on goal difference, and Simeone's side will be confident of avenging September's 2-1 defeat at home to Benfica when they travel to Lisbon next month.
The section winners will theoretically avoid any of Europe's big guns when the draw for the round of 16 is made on Dec. 14.
"We played impressively in line with the ongoing improvement of the team," Simeone told a news conference.
"As a concept, it is always better to be first than second, although it doesn't guarantee you anything," added the former Argentina captain.
"In the last 16 all the teams are competitive. We will go and play the match in Lisbon with the same intensity and abilities as always."
Griezmann has been Atletico's stand-out player this season and the France forward also scored twice when they won 2-0 at Galatasaray on matchday one in September.
The 24-year-old is in his second season in Madrid after joining from Real Sociedad and maintaining his fine run of form will be key to Atletico's chances of winning silverware.
"The important thing was to win (and qualify for the next round) but now we have another game to secure first place, which is the goal," Griezmann said. "We will go to Portugal to get that top spot."
Atletico are second in La Liga after 12 matches, four points behind leaders Barcelona and two ahead of third-placed Real Madrid, ahead of their next outing at home to Espanyol on Saturday.
(Writing by Iain Rogers, editing by Amlan Chakraborty)
