Mr Scadding has three grown-up children from a previous marriage, whom he said he has always told he would win the lottery one day.
He said he has been a "kept man" since Christmas due to a scarcity of work.
"I'm very lucky to be here, having suffered with cancer," said Mr Scadding.
"I think somebody decided I have got to wait until now because I'm going to win the lottery."
He said his daughter in Abu Dhabi was always ringing saying "Have you won the lottery yet?" and now he has.
Mr Scadding said: "I have never ever in my life owned a new car. So I'm going to buy a new car now. My dream car is a Range Rover Sport, black with ivory interior. Not that I've thought about it much!"
Mrs Peachey-Scadding is hoping to take things a little easier now.
She said: "There is quite a lot of pressure involved in running your own business, and I've been working 12 hours day recently.
"This win means I can take my foot off the pedal and relax a bit."
The couple, who married two and a half years ago and have been together seven, plan to move to a bigger house, but say they will probably stay in south Wales, although they may also buy a holiday home.
They also intend to splash out on holidays in Barbados.
It is the UK's largest-ever lottery prize and the couple are picking up their £45,570,835.50 cheque for half the jackpot.
Neighbour Ann-Marie Tait: 'They never said a word'
Caerleon has a population of around 8,700 and is around four miles from the city of Newport.
It is well known for its historic links with the Roman army, which had a garrison there. The National Roman Legion Museum is based in the town.
Ann-Marie Tait, who is the lottery winners' next door neighbour, said they were a "lovely couple" and "richly deserved it".
They had celebrated the win on Sunday at their favourite restaurant, The Priory, although owner Miguel Santiago had not known the reason for the champagne order.
"You can't help but say it couldn't have gone to a nicer couple," he said.
"They don't have a bad word to say about anybody.
"Les has come through thick and thin in recent years. He was out of work and things were difficult for them both."
The winning ticket was bought from the same store from which another lottery winner - Jenny Southall - won more than £8m in 2007
Until now, the biggest single win was by Angela Kelly, from South Lanarkshire, who won more than £35m (39m euros) in August 2007.
The winning numbers on the Euromillions draw last Friday were 19, 43, 45, 34, 11 and the Lucky Star numbers were 5 and 9.
A group of Hewlett Packard IT workers from Liverpool scooped the other half of last Friday's Euromillions jackpot.
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