Smart Content broken
For context; I just recently purchased a new laptop. However, I went a little messy with re-configuring all my content from my D-Drive onto the new computer. And now, within the "Content Library" tab under "DAZ Studio Formats", I now have two copies of both "My DAZ 3D Library" folder and the "My Library" folder (not copies necessarily, but two different pathways in which the products are being stored), which I assume is the root cause of products not properly showing onto the "Smart Content" tab. Only one of the folders appear within Smart Content and not the more-massive folder. Is there a way I can simply "merge" these folders together, or maybe have Smart Content go through all the folders within the Content Library? Or am I not correctly diagnosing the issue at hand? What would be the best course of action here?

Comments
You may have to post some screenshots as I am not sure it's 100% clear what situation you have ended up in. If you have two "copies" of each of your folders in Content Library then you'd need to address that first. I am not sure it's possible to add the same folders twice (but perhaps it is). Fix that part so you have each folder listed once under "Daz Studio Formats" - having the same folder listed again under "Power Formats" is fine. If you somehow have libraries within libraries then that must be fixed ASAP since it will break the asset loading regardless of anything else.
It's fine to have multiple seperate libraries linked to Daz. For instance I have three configured: the normal "My DAZ 3D Library" that DIM installs products to, "My Library" for anything I have created (renders, custom textures etc) and a "Third Party Library" for products from other stores. Daz copes with this with no issue. It has been said that perhaps if you have more than 10 then you may start to see a little bit of a slow down in some instances when loading assets but again that would probably be hardware-dependant.
Once you are happy that you have resolved the library mappings under COntent Library then you can fix the Smart Content. To do that go to the tab and select "Content DB Maintenance" from the corner menu. In the popup window you want "Reimport Metadata". This will scan all your libraries (hence the need to fix that first) and read in avery dsx file under runtime/support (including any previously-exported metadata). You'll see a list of all products it found with everything checked by default - you can look over this list if you like to make sure everything looks fine - then hit the button to continue and it will re-import all the metadata to the CMS database. It can take quite a while (20 mins the last time I did it) depending on the amount of assets you have and your hardware setup.
My Library and My Daz 3d Library are just default names, they have no functional significance - if you have two folders of each name connected then that is fine, if confusing for the human user. Most likely you don't have or have not imported metadata for the alrger library and that is why its files are not showing in Smart Content (or other database-driven views). If you open the Content Library option menu, the lined/hamburger button in the top corner, and select Content DB Maintenence then check Reimport Metadata and click Accept you will get another dialogue in which you can batch or individually pick products to reload the metadata for.
The issue is that DS checks each path in turn when trying to resolve relative references - that is potentially a lot of checks, so if files are in the later directories the process can slow down enormously.