Because Silverlight is client-side, it uses only WCF to connect to data sources. That means that it really doesn't matter what version of SQL you are using relative to what version of Silverlight you have. The two are not connected directly. This allows Silverlight to do what it does best (display and gather data and do other UI "stuff").
WCF, on the other hand, can use almost any data source you can dream of using. It can pull from MySQL databases, SQL databases of all versions, and basically anything else that it can connect to via code.
RIA is built on top of WCF so there are some limitations on RIA. There is a question that goes through this in some more detail: RIA Services Vs. WCF and Shared Code
So, the simple answer to your question is no, using SQL 2005 will not be a problem and no, there isn't a more direct way to connect Silverlight to your SQL database.