From my reading of things setting up MariaDB and activating TokuDB on a 64 bit Debian/Ubuntu server is a relatively easy task.
I currently use mySQL and have a great deal of (well written, I think) SQL in PHP that uses PDO to access the database. I gather that there are no syntactical differences between the flavors of SQL being used by MariaDB and mySQL. My questions
Finally, are there any other gotchas here that one must be aware of prior to making such a switch? I'd much appreciate any help.
You can do a mysqldump on your current MySQL database and use the output to load all your data into MariaDB. One goal of MariaDB is to be fully compatible with MySQL (for now at least) so you can usually shutdown your existing MySQL server, copy the data folder over to your MariaDB install, and start it up.
Given the compatibility goal of MariaDB, there is no need to switch your engine=innodb statements to anything else, it understands that innodb=xtradb.
Lastly, if you want to begin converting your tables to the TokuDB storage engine, check out the Quick Start Guide for tips.