Angels have the Phone Box
Windows 10 still has the compatibility mode selections. If that's how you got the program working in W7, you should be able to do the same in W10. What program is it, and what did you do to get it working in W7?
As far as cloning/imaging goes, I would recommend using Macrium Reflect Free, and make an image of your entire SSD (all partitions), and include the "verify" option when making it. Then, I would restore that image to the new SSD.
Using the "Get Windows 10" tool through Windows Update, it *should* give you a list of any incompatible programs before you upgrade, but I have seen OEM programs (considered bloatware) removed during the upgrade process, and not mentioned until after all is done; a message appears in Notifications telling you such-and-such is not compatible and has been removed. If you find it has removed your wife's special program, you could try reinstalling it at that point using the compatibility selections.
Since you technically have 30 days to make up your mind if you want to keep W10 or rollback, I don't believe your W7 key will be "consumed" at this point by the upgrade. I have heard many people making images using Macrium before taking the plunge to W10, in case the "rollback feature" fails. I can't think of anyone here on the forums at the moment who has actually restored an old image after upgrading off hand, though I'm sure there are some.
Hopefully someone will chime in here if they have done it. Hope that helps.