The 26-year-old fullback's close friend and former Indigenous All Stars prop George Rose told AAP it was "a fitting accolade".
"Latrell is a person who is proud of his culture and always represents his people on his chest every day of the year," Rose said.
Mitchell's South Sydney teammate Cody Walker was set to captain the side against the Maori All Stars in Townsville on Friday night but pulled out of the clash with injury, opening the door for his colleague.
"This means everything to me. To lead my people is an honour that I don't take lightly both on and off the field," Mitchell said.
"This week we celebrate our culture and get to go and express that in front of the whole nation. This is much more than a game to us."
Mitchell has Biripi, Wiradjuri, Worimi and Gumbaynggirr heritage and will play in his sixth All Stars match since 2017.
Indigenous All Stars coach Ronald Griffiths said Mitchell was the ideal candidate as skipper.
"Latrell is a pillar in our community and his work away from the limelight is unheralded ... a magical player who will go to the nth degree to make sure the All Stars camp is a success and leave a lasting impact in the community," he said.
Rose is a close friend and near neighbour of Mitchell's and has worked closely with him at Koori Knockouts over a long period of time.
The 2011 premiership winner said Mitchell, who recently revealed he found last season to be a mentally draining one, would thrive in 2024 at South Sydney.
Mitchell was in strong form at the start of 2023 before a long-term injury interrupted his season and he was unable to find his best at the end of the year.
"I'm proud of Latrell. I think he has put in a lot of work this off-season and the addition of Jack Wighton at the Rabbitohs has really sparked him back up," Rose said.
"It has lit a bit of a light in him again and you see the joy he has got in him both on and off the field. He leads with his actions and is a good father and man.
"It doesn't surprise me that they have chosen to put him forward as captain of the Indigenous All Stars side because Latrell plays with his heart on his sleeve and has got a lot of pride in his culture.
"I am pretty sure (the Indigenous All Stars) were just out at Palm Island, and getting to be part of the community he gets to see the people that he does it all for.
"He is one guy who a lot of guys in the Indigenous All Stars will be looking up to for what he does as a community man and a cultural man."
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