Australia go into their third successive finals as rank outsiders after a stuttering qualification campaign and a horror draw, where they were grouped with world champions Spain, 2010 runners-up the Netherlands and Chile.
Postecoglou, who succeeded Holger Osieck last October, will name his preliminary squad next week and is expected to put his trust in youth, having already told the leader of the golden generation, Lucas Neill, that he would not be going to Brazil.
"I was involved in 2010 and the turnover of players maybe should have happened earlier from the golden generation," Arnold, who was appointed manager of Sydney FC this week, told ABC radio on Friday.
"It didn't, and that's put Ange in a more difficult position. But knowing Ange, he'll do a great job and the players will be ready."
Arnold, who was caretaker Socceroos coach from 2006-7 and an assistant for the 2006 and 2010 World Cup finals campaigns, has coached many of the younger players likely to feature in Brazil at club level.
Despite their limited experience of international football, he thinks the likes of goalkeeper Mat Ryan, forward Tomas Rogic and defender Trent Sainsbury will not look out of place at football's showpiece event.
"Ange has stated from day one that he'll never be scared to give those kids the opportunity. Do they have the quality? I believe they do," Arnold added.
"Matty Ryan left here last year. He's gone across to Belgium and he's the best keeper in the league.
"I do believe and I have heard that he's getting interest from Real Madrid, he's been doing that well. That kid won't be phased by anything.
"Players like Tommy Rogic, and if Trent Sainsbury gets a chance, they wouldn't be phased by the occasion."
Arnold, the other leading candidate to replace German Osieck last year after Australia decided they needed a homegrown coach, backed Postecoglou to produce a team that would do credit to the nation.
"Ange is a guy who puts a lot of belief in the players. You can see the way they play football is that he always wants to give them opportunity to play," he said.
"I'm sure, no matter what team goes out there, they'll do Australia proud."
(Reporting by Nick Mulvenney, editing by Peter Rutherford)
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