Anthony Craig Westaway is behind bars on four charges of kidnapping and one of being armed with intent after police seized "several" weapons in a search of his Armidale home.

The 47-year-old was arrested by detectives and the Proactive Crime Team on Wednesday afternoon when the Kirkwood Street home was raided about 3.45pm.

In Armidale Local Court on Thursday, magistrate Michael Holmes refused bail because the offences were allegedly committed while Westaway was on conditional liberty.

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Police allege Westaway drove a getaway car from Armidale up the New England Highway to the crash site near Guyra on Saturday morning.

He was allegedly involved in kidnapping the couple, driving them to an Armidale location where they were held against their will until they escaped.

Lawrence Daniel Tafra is behind bars on 18 charges, accused of running the couple off the road about 5am on Saturday, and kidnapping them. He was arrested on Monday after a raid on a Marsh Street motel room.

He's admitted to drug supply and proceeds offences after about 25 grams of the drug ice was uncovered in his room, as well as more than $30,000 in cash which police claimed was the proceeds of his drug dealing.

Both men have been ordered to remain in custody until the cases return to court later this month.

Police have said investigations are continuing.

On Thursday, detectives made a fresh appeal for anyone driving on the New England Highway between Llangothlin and Guyra in the early hours of Saturday morning.

They specifically want to talk to anyone with dashcam footage who was in the area between 4am and 6am and might have seen the white Holden station wagon before it collided with a silver Holden Statesman.

It's the police case that Tafra rammed a silver Holden Statesman, which left the road and crashed, after rolling several times. The wrecks of both cars ended up down an embankment off the side of the highway, about 8km out of Guyra.

Police allege Tafra then kidnapped the couple inside - who were known to him.

Anyone with information is urged to contact investigators at Armidale police station on 6771 0699.