The Johannesburg franchise arrive in Cape Town on the back of the suspension of coach John Mitchell while they cope with the debilitating effects of an undecided Super Rugby future.
De Villiers said the hosts would nonetheless approach the match with the same caution afforded to the top teams.
“Every team in this competition is dangerous and you cannot afford to relax, as the Sharks found out to their regret when they lost to the Lions,” De Villiers said.
"They have as much desire, so we have to play well, and equally they have just as much to play for.
"At the start of the week, when we looked ahead at the fixture, we realised that we're in for a tough game."
De Villiers, like the rest of the returning Springboks, had the option of enjoying a break after three back-to-back gruelling Tests against England, but he opted to lead the side.
"For us Springboks there is a feeling that we finished the Test series on a negative note," he said.
"This game gives us a chance to feel better by putting in a good performance."
Stormers coach Allister Coetzee said he admired De Villiers for fronting up to the responsibility of captaining the side instead of resting.
“Jean was out for three weeks [prior to the Tests] with an injury so he was forced to rest, and even after the Tests he's still determined to play," Coetzee said.
"I wasn’t going to argue with him, especially since we're approaching the business end of Super Rugby.”
Interim Lions coach Johan Ackermann expected a tough contest from the SA conference leaders, and he said they would need to be prepared for a powerful Stormers side.
Ackermann's team are lying second from bottom with only two wins in the campaign.
"They are playing for a cup that they haven't won, so I think the motivation from their side won't be short," Ackermann said.
"We know it is going to be a tough ask and we are looking forward to a good challenge."