Gordon Strachan takes his side south of the border for the clash on August 14 bolstered by a shock World Cup qualifying win over Croatia in their last outing.
Collins earned his 58th and final cap for Scotland at Wembley in a 1-0 win in 1999 and sees no reason why the class of 2013 cannot produce a repeat of that result.
He said: "Of course we can win. In any football game it's 11 against 11. England are not, I don't think, the England of old.
"There is nothing to fear. They are respected but I think the key is to go there and believe you can beat them.
"We've got good players. There is no pressure when Scotland go there.
"All the pressure is on England. They will expect to beat little old Scotland.
"But they did that last time and we managed to get a 1-0 victory so hopefully the boys will go down there and put on a performance, do the Tartan Army proud and get a result."
The victory in Zagreb was the first in what has largely been a disappointing qualification campaign, with the Scots already well out of the running for a place at Brazil next summer.
Collins was in the squad who last graced a major finals - at France 98 - and he believes a positive start to the next campaign is crucial to finally end the wait to qualify for a top tournament again.
He said: "It will take a lot of hard work and a bit of luck.
"But Gordon has come in and had a fantastic result in the last game against Croatia.
"Obviously we are not going to get to Brazil but in the next major tournament our target at kick off is to qualify.
"We've never had a great start; in the last two or three campaigns we've had poor starts, which makes it difficult for everybody.
"Confidence goes and a lot of it is about confidence. We need a good start to the next campaign."