UPDATE `tablename`
SET `columnname` = 
TRIM(LEADING  'THE CHARACTER YOU WANT TO REMOVE, eg: A'  FROM `columnname`);

TRIM([{BOTH | LEADING | TRAILING} [remstr] FROM] str), TRIM([remstr FROM] str)

Returns the string str with all remstr prefixes or suffixes removed. If none of the specifiers BOTH, LEADING, or TRAILING is given, BOTH is assumed. remstr is optional and, if not specified, spaces are removed.

mysql> SELECT TRIM('  bar   ');
        -> 'bar'
mysql> SELECT TRIM(LEADING 'x' FROM 'xxxbarxxx');
        -> 'barxxx'
mysql> SELECT TRIM(BOTH 'x' FROM 'xxxbarxxx');
        -> 'bar'
mysql> SELECT TRIM(TRAILING 'xyz' FROM 'barxxyz');
        -> 'barx'

This function is multi-byte safe.

Source: MySQL 5.0 Reference Manual