Hemlock,
Sealing the grout line with a silicone sealer or another grout sealer will help keep stains to a minimum, and help a little with water peneration. I would go that route instead of trying to use plain silicone on everything. Also, some grouts have been fortified to help with this, but many people add the sealant as well. NEVER use grout sealants you SPRAY on.
To help, just make sure your tile edge next to the tub ledge is caulked with a blended silicone/latex caulk. Doing this in the corners next to in the lower portion is helpful. I really don't suggest just plain silicone because it is awful to get off, and difficult to control in a bathroom setting. The combo of silicone/latex works very well for joint areas.
Do you know what they used in materials behind the tile? Cement board or something else? Some tile installers who use cbu will also use something like a waterproof membrane that is a liquid you apply, In an older method, Some will just use a thick plastic behind the cbu. It depends on how much the tile installers keep up on the industry.