Carlo Ancelotti's men will be intent on securing a first-leg advantage ahead of their short trip to the Vicente Calderon when they host the Rojiblancos at the Santiago Bernabeu
The city rivals met five times in all competitions last term, including the Champions League showpiece in Lisbon - which Real won 4-1 after extra time.
Real also came out on top when the clubs clashed in the Copa del Rey - running out 5-0 aggregate winners in the semi-finals before beating Barcelona in the final - but Atletico had the edge in La Liga, taking four points off Real on their way to winning the title.
Carlo Ancelotti's European champions picked up where they left off last season by seeing off Sevilla in the UEFA Super Cup last week, and Atleti have also got their hands on some silverware already by winning the Ramon de Carranza Trophy.
While Real's win in Cardiff represents a bigger achievement than Atletico's close-season successes against the likes of Wolfsburg, Cadiz and Sampdoria, midfielder Mario Suarez feels his team-mates can build on last season's momentum - starting in Tuesday's first leg at the Santiago Bernabeu.
"We play every game like it's our last. Every game is important. The team played well and we felt good [against Sampdoria]," said Suarez.
"On Tuesday we have to play for an important title against our long-time rival and we'll face it as we always do.
"We'll go to win and everyone knows it. It will be very difficult."
Victory in the Supercopa would represent an ideal boost for both sides ahead of their Liga openers later this month - with Real and Atletico taking on Cordoba and Rayo Vallecano in their respective curtain-raisers.
Real ended their close-season friendlies with defeat to Fiorentina on Saturday - with their only win since lifting the Champions League coming against Sevilla in the Welsh capital last week.
Despite struggling for victories in recent weeks, big-name arrivals such as James Rodriguez and Toni Kroos have both got playing time under their belts alongside the likes of Cristiano Ronaldo and Gareth Bale.
Ancelotti's main selection dilemma for the visit of Atleti will likely come in goal with recent signing Keylor Navas and long-serving captain Iker Casillas vying for the number one spot.
"We'll make the decision on who plays in the Supercopa de Espana later on," said Ancelotti prior to the Fiorentina game, in which Navas made his Real debut.
The Italian may call on Bale (back) and Pepe (calf) for Tuesday's clash after they failed to feature in Saturday's loss while Ronaldo - who scored twice against Sevilla - also looks to have shaken off injury worries that dogged him at times last season and during the World Cup.
"He's [Ronaldo] ready for the Supercopa de Espana without any issues," Ancelotti added.