The Trinidad & Tobago Football Association, which announced the news of Samuel's death, said the collision occurred after he had dropped his children at school.
He played youth football for Charlton and joined Villa in August 1998, made his senior debut the following year and went on to make 199 appearances over nine years.
Aston Villa tweeted this afternoon to say the team would be wearing black armbands in tribute to Samuel in their play-off semi-final at home to Middlesbrough tonight. His vehicle caught fire and his body was discovered burnt.
'The Trinidad and Tobago Football Association and his former national teammates at this time extends deepest condolences to his family members both in the United Kingdom and here in Trinidad and Tobago'.
Samuel, who was born in San Fernando, played for Aston Villa Football Club in the United Kingdom from 1999-2007.
The former England Under-21 worldwide - who switched allegiances to Trinidad and Tobago in 2009 - came through the ranks at Charlton Athletic before playing for Villa, Bolton, Gillingham and Cardiff City.
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"Sadly the driver of the auto, Jlloyd Samuel, 37, from Lymm, died at the scene", a statement said.
"His next of kin have been informed and are now being supported by specially trained officers".
Samuel did not get clearance in time to join the Soca Warriors in Germany and it was another three years before he made his first senior worldwide cap in red, white and black strip.
Footballers' union the Professional Footballers' Association extended its "sincere condolences" to Samuel's family and friends, with the Football League saying it was "deeply saddened" by the news of his death.
It is understood that the man who was driving the van sustained serious injuries and was immediately taken to hospital for treatment.