The Baa-Baas, whose starting line-up boasted more than 600 Test caps, contributed to the entertainment with tries from full-back Matt Burke, wing Bruce Reihana and flanker Olivier Magne.
Barkley, Simpson-Daniel and skipper Pat Sanderson were the pick of an efficient, if unspectacular England side, and Australia will provide an infinitely tougher challenge at Sydney's Telstra Stadium on June 11, then Melbourne six days later.
England made a bright start, off-loading well in contact before Barkley kicked them ahead through a 38-metre penalty after opposite number Carlos Spencer was denied an interception try for offside.
Barkley doubled the lead with a second penalty and, predictably, England proved more structured and deliberate in attack than their opponents, but an opening quarter high on endeavour finished try-less.
The Baa-Baas looked poised to score after slick approach work created a two-man overlap, yet Reihana's pass was intercepted by Simpson-Daniel, who raced 80 metres unopposed for a gift try.
Barkley's conversion made it 13-0, although any hint of English complacency was immediately removed when Tait fumbled in defence and Magne capitalised by strolling over for his team's opening try, converted by Burke.
There was little pattern to the game, which suited the Barbarians far more than England, and Sanderson saw his team fall behind through a score that will have concerned defence coach Ford.
England were blown open in midfield by flanker Toutai Kefu's charge, leaving Burke with a simple task of sending Reihana sprinting over, with the conversion completing the wiping out a 13-point deficit during six damaging minutes.
The Baa-Baas had their opponents on the ropes, but the game's unpredictable nature meant another expected turn as Tait broke out of defence, scrum-half Peter Richards kept the move going and Simpson-Daniel stepped neatly inside two attempted tackles for his second try to edge England 18-14 ahead at half-time.
England fell behind again on 53 minutes, as a bullocking run by Cardiff Blues number eight Xavier Rush left England's defence at sixes and sevens, and quickly recycled possession saw Burke cross wide out.
Although the Australian could not convert, the Baa-Baas led 19-18, which was a cue for England boss Andy Robinson to make four switches, taking off centre Mike Catt, prop Tim Payne, hooker Lee Mears and lock James Hudson and sending on Stuart Abbott, Barnes, David Paice and Kieran Roche.
Barkley then gathered Spencer's speculative kick out of defence, racing 30 metres for a try which he converted, making it 25-19, and England ran pulled away during the closing quarter, scoring 21 further unanswered points to give them a record winning margin for the fixture.