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Since I removed the goldfish from the tank to make sure that any fry had a fighting chance (my goldfish are more like Koi Sharks than ornamental fish), the plecs have definitely been a lot more skittish. Before they'd happily feed during the day, they definitely are a lot more reserved now. Is this normal? If so, I shall have to think about getting some fry-friendly tankmates, and would welcome recommendations.

I assume the tank is unheated, and at room temp?

If so, try the Odessa barb, Puntius padamya. Any Danio, or the white cloud mountain minnow would work well too.

This is actually pretty common, you need some sort of dither fish for them, tetras or rasboras will work fine as they are peaceful and will not see any interest in the fry. The plecos become more reserved because they see no other fish in the tank and that sort of scares them, for lack of better words. But adding a few schooling, non-temperamental fish should do the trick, anything to liven up the tank basically. I keep a small group of 6-8 cardinals in most of my grow-out tanks. Adding dither fish will greatly improve the time they come out into the open IMO.

Dither fish - what a great description!

The tank is running 23 degrees, and I'm thinking about adding neon tetras, at least 6 to get a mini shoal, possibly more as time goes on. I was tempted by dalmatian mollies, but I do love the colouring of the tetras. I'm also thinking about cherry shrimps as well.

I'm not place any fish with my ancistrus.
They just see me a lot.

Shrimp may work but I would definitely get some sort of mid level swimming tetra. the neons or cardinals should work great. Good luck and hopefully this helped!

The tank is running 23 degrees, and I'm thinking about adding neon tetras, at least 6 to get a mini shoal, possibly more as time goes on. I was tempted by dalmatian mollies, but I do love the colouring of the tetras.

Mollies require brackish water, so are not a good idea.

I'd also say the tank is too cold for Amazonian tetras. Asian cyprinids such as those I mentioned will be a better option.

I've got a breeding pair of BNP in a tank with neon tetras and cories and they and the fry are doing well. Neither the Bandit coryies nor the tetras bother even the smallest emerging fry, and I've had monthly spawns since December.

I'm still looking at adding shoaling fish, but recently added a bunch of cherry shrimps, and got offered a load of juvenile bristlenoses at a great price (and got to see the tank they came from - all happy and healthy). Since their introduction the adults in the tank are a little happier, so a few neons will be going in shortly.

Got an unexpected bonus in the fish I picked up - one of the juveniles is definitely spotted, so hopefully I've got something a little different as a bonus.