The 30-year-old striker has experienced a number of big matches during his time in football, including the 2003 UEFA Cup final with Celtic and, more recently, two Wembley appearances with Wigan at an FA Cup final and Community Shield game.
And Maloney is expected to be named in a Scotland team to face England in a match to celebrate 150 years of the Football Association.
Looking ahead to the match, he said: "These fixtures don't happen very often but to play against England at Wembley is the most important international game I have played in and I will imagine it will be on a par with anything I have played in club football.
"So that's what it means to us and I imagine the majority of the country.
"I understand it is a friendly and some of their players will play 45 minutes and things like that but for us it will mean the world.
"We will certainly be going in as underdogs on Wednesday but hoping that we can get the result."
Back in June, Scotland enjoyed a creditable 1-0 victory in Croatia which was their first win in seven World Cup qualifying fixtures.
And Maloney believes the Scots must try and produce a similar display at England's national stadium.
He added: "We didn't play Croatia off the park, we worked hard and were very organised, got a goal and defended pretty well after that and if we are to get a decent result against England it will be something similar in that game."