De Villiers, returning to the side after an operation on his ankle during the off-season, will keep wicket in the one-day series as well as playing a critical role in the batting line-up. Heino Kuhn, who kept wicket for the two Twenty20 games, has been released back to his province.
The three-match series kicks off in Bloemfontein on Friday.
"If AB is going to keep (wicket), he needs to get his mindset right and he needs to know that he's got to commit to it 100% and see it as a future for himself in the shorter form of the game," Smith said.
"I still think management of AB is going to be key to his future. The pressures on him are going to get bigger and bigger in his career so it's crucial he's given as much support as possible in terms of his body and his mind.
"He's going to be one of our best players and carry a lot of the can for South Africa in the future. I think he's very capable of it but I think it's important he's provided with a lot of support."
The Proteas benefited this week from the experience of specialist consultants including Shaun Pollock, Lance Klusener, Ray Jennings and Duncan Fletcher, and the skipper said it had been "a massive positive" for the team.
"Just having their experience around was great, especially from a bowling perspective, having guys around like Polly (Shaun Pollock) and Lance (Klusener)," he said.
Smith said he hoped the younger members of the team would step up and make the most of their opportunities.
"I think when selectors make decisions it's always the responsibility of the players themselves to take those opportunities," he said.
"Our squad is in a good space at the moment. It is very inexperienced in many ways and you hope that the players who've been given the opportunities really take them and show that they deserve them."
Smith will not have the advice of players such as Mark Boucher and Jacques Kallis in the field, but did not see that as a problem.
"Having people to rely on in the field is always nice for a captain, but we've got injuries to experienced key players so I'm going to have to look to the young guys to really step up on the field.
"They're going to be bowling in the pressure situations and need to take responsibility and show they're capable of pushing for places.
"Over eight to nine years as captain, you learn that it's not a perfect world and so you learn to adapt and to take the positives out of every situation.
"For me, guys like Rusty Theron, Wayne Parnell and Lonwabo Tsotsobe have a real opportunity as they've been on the fringes for a while. I hope they take it with both hands and perform well."
Smith said their next eight ODI matches (three against Zimbabwe and five against Pakistan) should give them time to make changes and perfect the squad in the build-up to next year's World Cup on the sub-continent.
"By the time we face India (in December) we should have clarity," he said.