If it's a shower that's been (properly) waterproofed in about the last 20 years, there should be no chance of water damage. That's all taken care of by the waterproofing membrane that's hidden out of sight behind the tiles.
Silicon, like grout and tile, really plays no part in waterproofing, it's just there to fill a gap that undergoes contraction/expansion as the building moves.
Just strip it off, scrape the remainder off with a razor blade, clean the area really well (scrub with strong detergent solution, rinse off with water, wipe over with a cloth wet with metho) and use some Selleys or Sika brand silicon.
Aside from the tap test (tap on the tiles and see if any sound drummy) there's not really any non-destructive test for water damage. If you have an inspection camera you could possibly look inside the wall from the other side after drilling a small hole, assuming you have access to it, that is.