I don't know about the GoT BDs, but I've ripped a good number of other TV series. I'm always very careful to watch enough of each episode to make sure it's the number I think it is. Babylon 5 was the WORST about this. Many other series have the episodes in order. Others don't.
In the case of Undeclared, the first run of DVDs (which I own) are actually out of order in that the order on DVD, as presented by the menus, etc, isn't what the director intended. So I had to renumber those to be different than the DVD presentation order also. This stuff gets complicated for sure.
If you have a program that plays BDs on your computer (the actual spinning discs), I would use that to select each episode in turn, and then note the Title number that is selected. That way you can tie a Title # to an Episode # and be sure about which episode is which.
Good luck!
Brian.