US-based Smith, 33, has over a hundred England caps to her name and is one of the most feared playmakers in the world.
White, 34, has been a mainstay of the Arsenal and England defences since the 1990s and 2012 will also be one of the final major tournaments of an illustrious career for her.
Smith told Eurosport that she never expected to play in an Olympics — but was looking forward to the prospect immensely.
"The World Cup has formed the pinnacle of my career, whereas the Olympics are different because I've never had the opportunity to play in one," she said.
"The two are not comparable. The Games are a global event, with many different sports - and they will be amazing because I never envisaged taking part in them.
"It's an extra added incentive at the end of my career. Speaking to a lot of the American girls, they view it as the ultimate, bigger than the World Cup."
White believes that London 2012 offers a unique opportunity for the girls of England, Scotland, Wales and Northern Ireland — with the 2011 World Cup in Germany a perfect example of what can be achieved.
"Team GB want to medal and be competitive at the Games," she said. "They are on home soil, so we have experienced the environment before, and the matches are taking place in the best football stadiums in the country.
"It is a golden opportunity to showcase the women's game in this country by entertaining the fans: the last World Cup showed how the level of women's football has improved, as you saw with the way the fans turned out in Germany."
"The fans will take the tournament to their hearts and hopefully the public will support us in numbers," she said. "The Games are in our own country - this won't happen again in our lifetime.
"It's a great opportunity, and hopefully we will do ourselves justice - and change opinion on women's football in this country."
The British team, coached by England manager Hope Powell, will mostly be made up of players from that country. It will be the first time that a 'Team GB' has contested a major tournament.
Smith is of the opinion that the women's tournament, featuring the greatest talent in the world, will be an even greater spectacle than the men's — which is U23 with three over-age players allowed per team.
"The majority of the team will be English, with a couple of additions from the associate nations," said Smith. "It will be a bit weird playing with those girls and representing Britain, not England, as we're not used to it.
"But we all know the same system, so I'm sure Hope Powell will use a similar one in leading the GB team. We try to play through the thirds, a possession-oriented game.
"The tournament has the top elite women's players, showcasing the best talent in the world, whereas in the men's game there will be none of your Messis and what have you.
"But the British team will have a great player in David Beckham, if he is fit!"
White is looking forward to experiencing the Wembley roar as a player as she nears the end of her career.
"I'm getting towards the end of my career and this will be a new experience for me: it could be a crowning glory," she added. "I'm not going to go on for too much longer afterwards.
"It's in you mind when you train every day - I've been to Wembley loads and heard the roar of the crowd, but what would it be like on the pitch?
"We're hoping for massive numbers for the home matches, with the crowd right behind us. The third game is there on July 31st - and potentially a semi-final and the final after that.
"On the 25th we play the first game of the Olympics, at the Millennium Stadium, with the men's game on the same day - a double header.
"And we also play at the Millennium Stadium on the 28th… tickets are still available to buy until February 6, but are selling fast."
Smith, regarded as the greatest female player the country has ever produced and perhaps featuring in her final major tournament, added: "Sell-out crowds in England are something we have never witnessed in the women's game in this country: in the 2005 Euros here the crowds were decent, but things were just getting going for us.
"If we have the support of a packed Wembley and Millennium Stadium, that will help us immensely."
- Sports & Recreation