Federal relief payments of up to $1000 are now available for residents of 29 local government areas, while NSW residents are being urged to donate money to GIVIT so help can be better coordinated.
As rain returned in areas across the state, including Sydney, authorities warned of several road closures and public transport disruptions due to flooding,
Some 37,000 people remained under evacuation orders on Saturday as the State Emergency Service said it was working through easing its emergency notices.
"There's obviously ramifications with that. It's not just a free-for-all, run back in there," Adam Jones from the SES told AAP.
"There will be debris, their homes won't have been checked, so if it has been inundated, there could be structural issues.
"The electrics might need to be looked at by an electrician. There could be mud and sewage everywhere."
Flood-affected residents returning to properties should wear PPE, boots, gloves and have sanitiser handy.
Mr Jones also urged people to mentally prepare to see their homes significantly damaged, and to reach out for community support.
"Everyone's going to be a bit stressed under these circumstances," he said.
The federal government expanded the number of areas able to access relief payments on Saturday evening, adding six more flood-affected councils to the list.
Payments of $1000 per eligible adult and $400 per eligible child are available to people impacted by the flooding.
Recovery efforts in the state will be overseen by former detective Dean Betts and fellow Resilience NSW director Mel Gore, Emergency Services Minister Steph Cooke said on Saturday.
"These appointments will help to ensure flood-affected communities receive support in a timely and efficient way," Ms Cooke said.
Flooding continued in the Hunter and lower Hawkesbury regions on Saturday, with more than 1000 government personnel on standby to assist.
Some 37 Victorian emergency personnel also travelled to NSW to help with the rescue and clean-up, taking the total number of crew from the state to 94.
Ms Cooke said the immediate priorities were damage assessments and making sure displaced residents could access emergency accommodation.
On Sunday, Ms Cooke said the GIVIT donation hub would allow the NSW government to better direct donated money for flood victims.
"By donating through the official channels people can know their generosity is going directly to those who've been hit hardest by the flooding," she said.
Of 2285 premises already examined, 239 have been deemed not habitable and a further 973 require repairs.
The NSW Department of Primary Industries also gave beekeepers another seven days to move hives to higher ground in flood areas.
NSW is battling an outbreak of hive-destroying varroa mite, with a stop on all hive movement.
In the Hunter, lower Hawkesbury and Blue Mountains regions, roads remain cut in multiple towns and train services are affected.
The T1 Western, Blue Mountains and Hunter train lines are not operating between some stations, and the Parramatta River ferries are offering replacement transport between some stops.
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