Moving libraries is easy:
Apple's 6 pages of exhaustively meticulous step-by-step instructions: How to move your iTunes library to a new computer - https://support.apple.com/HT204318 Use this if you suspect any of your media are not in the standard location (iTunes Media folder).
My one-sentence summary if you always use iTunes' default preferences settings: Copy the entire iTunes folder (and in doing so all its sub-folders and files) intact to the other drive, hold down the option/alt key (shift on Windows) while starting iTunes, and when requested to select a library select the iTunes Library.itl file in the copied folder (Open a different iTunes Library file or create a new one - https://support.apple.com/HT201596).
When this is to a new drive/computer put the copied iTunes folder in the default location of Macintosh HD > Users > *User Name* > Music (or Home > Music) then you don't even need to start with the option key held down, iTunes will automatically look for it there. (Make sure there isn't anything already in the iTunes folder there that you want to keep since you will be replacing it with the one you are moving.) Remember to authorize the computer in iTunes to your Apple ID if you use this to sync to Apple mobile devices or play DRM protected media (e.g., movies).
Merging libraries is not easy. Basically you have to add media from one to the other, then spend a day or weekend or week sorting duplicates (unless you can do this prior to adding).
I don't know about Windows machines but using a NAS with iTunes on a Mac is inadvisable. NAS and iTunes behave erratically and can lead to strange errors that are not readily explained or solved.