Attaining his first cap in 1996, Blain became Scotland's youngest-capped cricketer since 1890. He played during the 1996 European Championship taking seven wickets at 9.85. Blain was initially signed as a footballer to Falkirk but decided to switch to cricket, signing for Northamptonshire, having not made an impact as a footballer.
He played for Yorkshire League side, Rotherham Cricket Club in 2007, and was due to sign for the Scottish League side, Ferguslie, in 2008. The move fell through, and Blain played for the Scottish Saltires and Rotherham.
He appeared in all Scotland's games at the 1999 and 2007 World Cups. He finished the 1999 event with 10 wickets at 21 with a strike rate of 22.3, the best in the tournament.
In the 2010, Blain made a solitary appearance for Yorkshire in the County Championship, and in both that campaign and in 2011, Blain was the regular captain of Yorkshire's Second XI.