In Python I'd like to redirect the location ArcGIS looks for SDE connection files when "Database Connections" is used. Is that possible?
"Database Connections\\GeoStore.sde"
The database connections section seems to put the database connection files here - C:\Users\username\AppData\Roaming\ESRI\Desktop10.2\ArcCatalog. Not sure if you can change where that goes to off the top of my head. What you could do is just copy your database connection files to a folder somewhere (e.g. C:\Data\Database Connections\GeoStore.sde) and reference that filepath.