I notice in the MSDN documentation that there are multiple ways to declare a reference to a function in an external DLL from within a VB.NET program.
The confusing
Declare is really an attempt to maintain a P/Invoke syntax which would be more familiar to Visual Basic 6.0 users converting to VB.NET. It has many of the same features as P/Invoke but the marshalling of certain types, in particular strings, are very different and can cause a bit of confusion to people more familiar with DllImport rules.
I'm not entirely sure what the documentation is alluding to with the "rare" distinction. I use DllImport in my code frequently from both VB.NET and C# without issue.
In general, I would use DllImport over Declare unless you come from a Visual Basic 6.0 background. The documentation and samples for DllImport are much better and there are many tools aimed at generating DllImport declarations.