The former Spain international is preparing to lead the Camp Nou outfit into Europe's elite club competition for the first time, beginning with a home fixture against APOEL on Wednesday.
Paris Saint-Germain and Ajax complete the line-up in Group F, but Luis Enrique refused to rank potential glory in the Champions League over domestic success in his debut campaign.
"For me it would be great to win either - not forgetting the Copa del Rey," he said. "It's the start of the season and we're going to fight to win them all. Let's hope we do win one and deserve it.
"I can't tell you I'm even one per cent more nervous [for the Champions League] than I have been before any other game this season.
"When those little stars come up, that music - it makes no difference to me.
"Really, it's just me doing my job as a coach.
"Maybe for the players this is different because you're stepping onto the big stage, but as a coach you are just managing the team."
The 44-year-old also resisted setting a target for Barcelona, who were knocked out at the quarter-final stage by eventual runners-up Atletico Madrid last season.
"Having a minimum expectation, judging by the way this club has performed in recent years, would be senseless," he stressed. "We have to go out to win every game."
But Luis Enrique conceded he was looking forward to making his Champions League bow as a coach.
"Of course it's special because of the competition," he said. "I think the team is in adequate condition for the tournament.
"There are a lot of things we need to improve, but there are also a lot of positive things.
"It's only early in the season, so we're not in our full rhythm yet. That could catch us out."
Luis Enrique also confirmed that Dani Alves should be available for selection after recovering from a knee injury.
Barcelona have won all three of their La Liga matches so far this season.
