There are unlikely to be any issues with the content store, as that contains the unmodified file content (which is the same regardless of the CPU and memory architecture - 32 bit vs 64 bit). The MySQL upgrade is where I would be most cautious - perhaps backing up the current 5.0.25 database, restoring into a 5.0.25 database on the 64 bit RHEL5 box, then upgrading MySQL to 5.1.x. I'm also not sure of the implications of moving from 32bit MySQL to 64bit MySQL - the MySQL documentation, forums etc. should be consulted for that information.
In general, taking a larger number of smaller, incremental steps is preferable to executing a single "big bang" step, as it's more efficient in the case where something goes awry somewhere along the line, and migrations / upgrades such as this one are no exception to that rule.
Cheers,
Peter