After some testing the error appears to be related to corruption of local save data. I've found a solution which works across game restarts.
Exit Pillars of Eternity.
From Steam, Control + Click on Pillars of Eternity from your Library.
Select Properties.
From the Updates tab, ensure the checkbox under the Steam Cloud section is checked.
(If this is not checked, you will need to enable it, restart PoE, and save your latest save. The game will crash on save but your save data will sync to Steam Cloud.)
Open Finder.
Click the Go menu.
While viewing the Go menu, hold Option. This will display the link to the Library folder. Click Library.
Navigate to /Application Support/Pillars of Eternity/Saved Games
Select all the saved game files. Control + Click and Move to Trash.
(This removes your local save files, however they can be retrieved from the Trash if you need them.)
Keep the Finder window open at the Saved Games folder, and start Pillars of Eternity from Steam.
You should see your saved games repopulating from Steam Cloud before the game begins.
Voila. You should also notice that the game loads the saved games at the main menu more quickly.