Williams, 25, will complete a meteoric rise through the ranks of New Zealand rugby on Saturday when he strides out at Twickenham in front of an 82,000 capacity crowd, barely two years after switching to rugby union.
But McCaw told reporters there was no question of the 6ft 4in (1.93m) 17 stone (108kg) centre former New Zealand rugby league international being overawed by the occasion.
"It’s a bit new to him being in the All Blacks and he wants to do well and I guess there's a few nerves because of that," McCaw said.
"Like anyone playing their first cap he’ll have those sorts of emotions but I’m sure he'll handle it.
"He's been in big games before. He's played international league and in Europe, it won't be a big issue."
McCaw meanwhile revealed Williams had been seamlessly integrated into the All Blacks set up since joining the squad.
"I've been really impressed over the last two weeks how he's fitted in. He's picked up everything we’ve been doing pretty easily. I guess I saw that when he was playing for Canterbury," McCaw said.
"He wants to learn, he’s pretty quick to ask questions. I’ll guess we'll see on Saturday but I've been pretty impressed."
While much has been made of Williams imposing physical presence, McCaw said he had been impressed with the centre's ball skills.
"He doesn’t just want to be a crash man," McCaw said. "He's got the ability to distribute."
New Zealand head into Saturday's Test still smarting from their last-gasp Bledisloe Cup defeat to Australia in Hong Kong last week.
McCaw said the New Zealanders would have no excuses for failing to hit the ground running against England.
"Last week you could use all sorts of excuses about not playing for a while and not being together," McCaw said. "This week there's none of those. We need to make sure we start well.
"The physical challenge will be different to last week. We have to start well and give ourselves an opportunity."
McCaw also declined to be drawn on the war-of-words which was triggered this week by England defence strategist Mike Ford, who disparaged this season's high-scoring Tri-Nations campaign as "not real rugby."
Instead McCaw said the All Blacks were preparing for a physical battle against the English, who are attempting to score only their seventh win in history against New Zealand.
"I just think back to the tests we’ve played against England in the past," McCaw said. "They’ve been physical battles but there’s opportunity to play.
"The way the rules are it allows good rewards for having good go-forward and good ball in hand. I don’t think Saturday will be much different from the past."
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