Samuel made 169 Premier League appearances for Villa and also had a four-year spell with Bolton in the top-flight.
He represented Trinidad and Tobago at senior level having won England Under-21 recognition, and most recently was manager of non-league Cheshire club Egerton guiding them to promotion.
Samuel, 37, was returning home in England after dropping his kids off at school before the tragedy.
Samuel was killed in a vehicle crash on Tuesday morning in the north west of England, the Trinidad and Tobago Football Association announced in a statement.
Villa, for whom Samuel played 199 times, primarily at full back, said its players will wear black armbands as a mark of respect in tonight's second leg of their play-off semi-final against Middlesbrough.
He attempted to switch worldwide allegiance before Trinidad and Tobago played at the 2006 World Cup in Germany.
Lewis Hamilton not getting carried away despite dominant Spanish Grand Prix win
The guys have been working so hard back in the factory and here and it's so good to see. He said: " If you're happy with your wife, you don't look at other women ".
He played youth football for Charlton before joining Aston Villa, where he made almost 200 appearances between 1999 and 2007.
Although his application was rejected by Federation Internationale de Football Association because he was over 21 at the time, he later represented the country of his birth.
He made his debut in 1999 and went on to make close to 200 appearances before joining Bolton in 2007.
Emergency services remain at the scene of a serious collision involving a van and a auto in High Legh.
Samuel celebrated his 37th birthday in March this year.
It is understood that the man who was driving the van sustained serious injuries and was immediately taken to hospital for treatment.