Samuel is understood to have dropped his children off at school before his vehicle collided with a truck on a country lane near Warrington.
The former England Under-21 international - 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.
Samuel then spent a stint in Iran before moving back to England and most recently managing non-league Cheshire side Egerton.
"We've received some terrible news that former National defender and Ex-Aston Villa and Bolton Wanderers player Jlloyd Samuel died in a car crash this morning in England," read a statement on the official Facebook page of the Trinidad and Tobago FA.
"According to reports, Jlloyd was returning home after dropping his kids off to school and collided with an oncoming vehicle.
"The Trinidad and Tobago Football Association and his former national teammates at this time extends deepest condolences to his family members both in the UK and here in Trinidad and Tobago."
Samuel made almost 250 Premier League appearances during his playing career, as well as winning two caps for Trinidad and Tobago.