By saying "...I am fairly comfortable with relational database...", have you done any database programming in pre-.NET era (VBA, classical VB...), or .NET data access programming?
Now that you are asking in this Acad .NET discussion forum, naturally, you would use .NET data access technology (ADO.NET) to directly access data in a database (either file based, such as MS Access, SqlLite.., or server based, such as Sql Server, MySql...). So, you need to firstly do some study on ADO.NET. There are a lot tutorials available online/Youtube.
Now comes to database of choice. IMO, MS Access is not a good (if not the worst) choice one would choose to work with custom AutoCAD application. The only time that is OK to choose it is that the user computer has already had 64-bit MS Access DB Engine installed by company computer setup requirement (say, as the result of 64-bit MS Office suite, which includes MS Access). Otherwise, in order for AutoCAD application to access data in MS Access, the user computer must have separate 64-bit MS Access DB engine installed, which is very tricky/difficult, if the use has 32-bit MS Office suite installed (it is most likely). So, by using MS Access, you simply add an unnecessary/difficult dependency to your CAD application.
For small data set, for the mobility reason, you can choose SqlLite, which is file based. If your CAD app is used in a office environment for multiple user, you might consider use server based database (such as SQLExpress), the extra benefit of using database server is that the dependency to the database server would make your CAD app sort of "theft-proof": no one can use it (or user it properly) without having access to the database server.