Former detective Dean Betts will oversee clean-up and rebuilding efforts in Greater Sydney, while fellow Resilience NSW director Mel Gore will take charge of operations for the state's Central Coast, Hunter Valley and mid-north coast.
"These appointments will help to ensure flood-affected communities receive support in a timely and efficient way," Emergency Services Minister Steph Cooke said on Saturday.
As floodwaters continue to recede, more than 1000 government personnel are on standby to assist with the clean-up.
Ms Cooke said the immediate priorities were damage assessments of flooded homes and businesses, and making sure displaced residents could access emergency accommodation.
From 2285 premises already examined, 239 have been deemed not habitable and a further 973 require repairs.
Some 37 Victorian emergency personnel will travel to NSW on Saturday to assist with the rescue and clean-up operation, taking the total number of crew from the state to 94.
The latest deployment includes 26 members of the VICSES and 11 swift water rescue specialists from Fire Rescue Victoria, with some volunteers to be sent to the Gosford and Maitland areas.
"Our neighbouring communities in NSW are suffering from an extreme and devastating weather event, so we will of course lend a helping hand during this difficult time," Fire Rescue Victoria Commissioner Ken Block said.
Government recovery centres across Greater Sydney, the Hawkesbury-Nepean Valley and Central Coast will open in the coming days.
Some 37 LGAs across NSW remain under natural disaster declarations, while SES Commissioner Carlene York has signed "transition to recovery" handover orders for those covering Camden, Canterbury-Bankstown, Fairfield, Liverpool, Penrith and Sutherland.
Meanwhile, Premier Dominic Perrottet is hoping the federal government will commit to half the funding required to raise Sydney's Warragamba Dam wall.
"This is a project in the billions of dollars. It is not a simple project," he said on Friday.
Mr Perrottet said in light of the flood crisis, he wanted to push ahead with the initiative despite the state being warned to pull back from major infrastructure initiatives during the current economic turbulence.
Labor leader Chris Minns said he was sceptical about raising the dam wall and wanted to see more money thrown into evacuation routes for flood-affected areas.
Back-to-back sunny days have sparked warnings from authorities not to think the worst of the floods are over, with waters still high and the risk of landslips remaining.
As of Friday, about 47,000 NSW residents remained under evacuation orders, with 50,000 being told to return home with caution.
Flooding continues to affect the Hunter region, with roads cut off in multiple towns and train services affected on the Hunter Line.
On the Hunter Line, no trains are running between the Newcastle Interchange, Scone and Dungog, and many buses are diverted or missing stops on Saturday.
Road closures are in place in Tomago, Raymond Terrace, Thornton, Millers Forest, Maitland, East Maitland, Branxton and Mitchells Flat.
The Newcastle and Central Coast rail lines reopened after heavy rain disrupted services between Cardiff and Wyong, but passengers are advised delays may be ongoing.
A number of roads reopened on Saturday in the Hawkesbury, including the Windsor Bridge and Wilberforce Road at Windsor.
Flooding also continues to affect some roads in Greater Sydney, with closures at Heathcote Road, Pitt Town Road and the Yarramundi Bridge.
The T1 Western and Blue Mountains train lines are also partially affected, as are the Parramatta River ferries.
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