"Those people that are responsible for this crime are truly evil and must be quickly caught and held to account for what they've done."
He said Karlie Jade and Khandalyce came from a loving family and spent much of their time in Alice Springs.
"During 2008 Karlie Jade and Khandalyce moved away from their family and started to travel and over time contact with the family became less for reasons that are not yet apparent to us," he said.
Supt Bray said Karlie Jade's mother had reported her daughter missing in 2009.
He said the last confirmed sighting of Karlie Jade was on November 8, 2008, on the Stuart Highway just south of Coober Pedy.
"At that time, Karlie was aged 20 and Khandalyce was aged two," NSW Police Detective Superintendent Mick Willing said on Wednesday.
A month later there was an unconfirmed sighting of the pair in a shopping centre in the ACT, he said.
In 2010, a woman's remains were discovered by trail-bike riders at Daly's Waterhole in the forest, south of Sydney.Nearby was a T-shirt emblazoned with the word "Angelic" in pink text, surrounded by a rose, heart and wings - with the victim becoming known as Angel.
NSW Police and SA Police have now entered a formal investigation into the deaths after DNA linked the two remains.
Both deaths have been described as "violent and deliberate" but police would not comment on the cause of death.
Supt Bray is urging the public to help in the investigation.
"It's about the murder of a little girl and everybody in our community must get behind the family and the police and provide whatever information they have about this," he said.
"The friends and associates, it's important we know them. We encourage them to make contact through Crime Stoppers."
He said the mother and daughter were at different times in Darwin, Alice Springs, Adelaide and Canberra.
"We know they've stayed in motels, caravan parks, along that route and other areas and possibly through the Murray Mallee and Riverland.
"We're asking that all landlords, motel operators, caravan park, cabin parks have a look at your records, everything's on computer, it's not hard."
Supt Bray said when another caller was then able to provide a photograph of a child dressed in a pink dress, similar to the one SA police had issued after the bones were found in July, it was quickly ascertain to be Khandalyce.
SA investigators, who had been in contact with NSW police, were aware of the skeletal remains in the Belanglo State Forest and the similarities in the description.
He said DNA analysis was done in Adelaide, which provided a profile that was matched to the skeletal remains.
The skeletal remains were confirmed to be Karlie Jade Pearce-Stevenson, who was born in Alice Springs in 1988.
"It's absolutely baffling. These cases are a mystery," Det Insp Willing said.
- AAP