Well of course it depends. I think a good rule of thumb is that the greater the volume of data you are working with, the more useful it is to know advanced topics. Pivot tables, for example are really only useful when you have a lot of data. Most things in Access are as well.
SQL is useful and easy to learn, as well as being found in many contexts. Macros (VBA) are very useful, but harder to learn.
In general, assuming you are competing against other people for a job, more advanced skills give you an advantage.
In terms of Excel vs Access, Excel is used in a much broader variety of situations.
So in short, given a general situation and not a specific job, I would say the order of priority is:
1. Basic Excel
2. Intermediate Excel (e.g. vlookups, filters, sumifs, pivot tables….)
3. Basic Access
4. SQL
5. VBA/Macros
Of course, this is just my opinion. I work in a very data- and calculation-intensive field; perhaps in a more standard office situation there would be a different set of priorities.
Hope this helps.