Assuming that the indexes are 100% accurate, then the Marriage Finder will be 100% accurate, given that the spouse will always have the same Volume, Page and Quarter as the input person.
However, please note that the output is usually a list of marriages - if you are looking for a marriage of a named bride in a specific district and quarter, then the best that you will get is a choice of 2 grooms, who are the 2 grooms on that page. If there are 2 brides with those details, you will get 4 potential grooms.
Even if you supply the name of John for the groom, you might get multiple choices if both grooms on that page are named John.
NB most GRO pages contain 2 marriages - I have an idea that the earliest had more, so that you will see more options.
If indexes are mistranscribed, the marriage finder will not be accurate.