The first south Wales derby in Barclays Premier League history takes place at Cardiff City Stadium on Sunday in front of a sell-out crowd and a huge global TV audience.
While there has been an increase in the spotlight on the game, Williams is something of a veteran of the battle for local bragging rights, having faced the Bluebirds on seven previous occasions.
The visitors can expect a hostile reception but Williams insists his men will not step back from the challenge.
"I enjoy playing in the derby games at home because you are in front of your home fans, but it's also nice to play away from home because you feel like you are behind enemy lines," he said.
"It is a bit different when you get off that road near the ground.
"You come down the hill and they are all lined up. They are not very pleased to see you.
"It's such a big game for us in our calendar and when you pull up at the ground, in the coach, it is a little bit different to when I pull up for a Wales game.
"You are there, they don't want you there and they let you know that.
"But that's why we play the game. None of the guys are going to shy away from it. We will all be up for it."
As Swansea skipper, Williams, who has won three, lost two and drawn two against Cardiff, can expect as much stick as anyone.
And the 29-year-old sees no reason why the captain of Wales should be exempt from any booing in the principality.
He said: "It's not nice but I'm used to it now.
"I think it's natural to be honest. It's not like I'm going to go there and play for Swansea and they will say 'actually, he is captain of Wales'....
"I know it's going to happen, but it's no big deal. Whenever I play for Wales now I always feel supported at that ground so that's not a problem.
"But I know if I go there with a Swansea shirt on, I am going to get booed.
"Whether or not it is louder than any other player I don't know. However, I'm ready for that."
Williams is expected to be partnered by Chico Flores at the heart of the Swansea defence on Sunday, in what will be the Spaniard's first derby experience.
And Williams has revealed his colleague has had an unconventional way of preparing.
"This week we have normally had Chico shouting 'Cardiff' at random times through the morning," he said.
"He just shouts that - he seems quite excited. We don't know exactly what he means, but we don't normally know what he is talking about anyway!
"It just shows that all the boys know how important the game is, whether they have played in the derby before or not."