Identifying sedimentary rocks in hand specimen
When learning to distinguish between siliceous and calcareous samples you should use a handlens.  Look for quartz, feldspars or micas.  Quartz clasts may be frosted, or you may be able to see conchoidal fracture.  Calcite will be very soft compared to both feldspar and quartz, and should fail to scratch copper (or at least not scratch it very well, while a quartz rich sedimentary hand sample will scratch glass.

For really fine grained stuff, there are times when you may need to use the context of site where the sample is from if you don't have HCL.  There can be sedimentary rocks that are made up of siliceous clasts that react with HCL due to calcite in the matrix, so HCL can be misleading.  I've even found that some mudstones and limestones can have an organic odor.

Lastly, there are structures that can suggest if a sample is siliceous or calcareous.  Styolites would suggest non-siliceous while thermal alterations like liesegang banding would suggest siliceous.

The more samples you tackle, the easier it gets.