Walker, last season’s PFA Young Player of the Year, is expected to replace the suspended Glen Johnson at right-back against San Marino.
And the Tottenham defender has credited the former Manchester United and England full-back with aiding his development and knowledge of the position.
"I'm young, I want to improve, I want to become the best I can be and Gary Neville is really helping me with that aim,” said Walker at an England press conference.
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"I've always liked to go forward but he has helped massively in terms of myself improving defensively. I just want to keep on learning."
Walker missed out on a place at Euro 2012 with a toe injury, but now hopes to make his first competitive start and establish himself in the national team.
"On a personal note it is a fantastic opportunity for me to get into the team,” he added. “I've been patient and waited for that.
"Hopefully on Friday I can show everyone what I can do and have a good game.
"A first competitive start is what I've been waiting for, for a long time now. For all my career, since I was seven, I've wanted to play for England, and put that jersey on.”
If he starts, Walker will not be expected to do much defending against San Marino, but team-mate Joe Hart warns England cannot afford to lose focus, regardless of the opposition.
"Concentration is always key," he said. "International football is not often 'you have a go and then we'll have a go'. It's a chess game.
"I imagine, like most teams when they come to Wembley, San Marino are going to try and get people behind the ball."
The Three Lions sit third in their qualifying group, after winning away in Moldova before drawing at home to Ukraine in September.
Three points will be expected on Friday but, with a tricky away fixture with Poland on the horizon, England's No.1 is looking for the side to step it up and qualify as soon as possible.
"We really need to push on from here," he added. "You have got to look to win all your games until you have potentially qualified.
"In the group stages, when you are qualifying for a World Cup, you know there is so much for the taking but there are not that many games and you have to get things right.
"We'll start by trying to do that on Friday after a good battling point against Ukraine in the last game."