Mostly confirming what was already said, but I've done a few panel replacements. The largest being a 100" x 24" piece on the back of my large tank's overflow. Depending on the size of the chip you might just leave it, but if it's large enough to be concerning then yes, replace it. If it has a rim make sure that comes off nicely. If not you might end up having to replace that too, or worst case breaking another panel getting it off.
1. As stated, new silicone doesn't like sticking to old silicone. You'll want to get all of it off and scrub the surface with some acetone or such to get the surface clean.
2. Momentive RTV100 series is what you want. RTV103 for black, RTV108 for clear. There's a white and silver as well, but I don't see those looking as nice. Be aware that this stuff skins over VERY fast. While the tack free time is around 20 minutes, my experience was that it was a noticeable change by the 2 minute mark. The first time I used it I laid down a 68" or so bead as quickly as my amateur self could, and immediately placed the glass. The end I started at already had a slight skin that needed to be broken as I placed the glass. Grainger, home of over-priced things used to actually be the cheapest common source. However, McMaster Carr has it now. Part number
7545A462 for black and
7545A472 for clear.
3. The next time I used this I opted to inject the silicone into the gap. I fixtured the panel where it needed to end up with a zillion clamps, then went along it and injected the silicone. This worked much better. It's a tad tedious and requires more prep, but the results were better.
4. Tape your seams on the inside. I've done it with and without this, they really do turn out MUCH nicer looking if you do. By this I mean putting tape a bit back from the edges. After you're done filling the seam you can smear your fillet just past the tape, wait just a minute or two, then peel the tape. You'll get nice clean lines in the silicone. Don't wait too long or it'll start curing up and you'll tear it a bit when you remove the tape.
5. I got my glass from Glass Cages, which was substantially cheaper than my local sources, but it looks like there's a better local source above, so I'd go with that.
6. Make the edges match whatever the rest of the tank is. I had one bad experience with a glass store back in Texas where I specified ground flat and polished. They interpreted this as polished, but there was a substantial curve along the edge which was a real pain.
7. Assuming the tank was designed to survive it, non-tempered gives you more options. If it chipped and didn't shatter the odds are to non-tempered. This is easy enough to check for with a cell phone screen set to white (ie a polarized light source) and a pair of polarized glasses. Note that this doesn't always work through a case or screen protector.
8. If you want drilled holes put them in before you glue it.
9. If it 's a front (or eurobrace), consider low iron.
10. Exact dimensions are important.