In fact, 19/34 is the “standard” stuff, but much, much finer is available. For example, Kabeltronik LiFY 20AWG (0.5mm2) has 256 strands of 0.05mm diameter, which is about 44AWG.
Fine-stranded silicone wire will be much, much more flexible than standard PVC. The downside is that silicone is not as abrasion resistant, so you have to keep that in mind with your mechanical design.
Also bear in mind that even within PVC with the same stranding there are big differences in flexibility. For example, the Chinese 24AWG I have is substantially less flexible than the European-made stuff ordered locally. But even that varies brand to brand.
As for your dotstar chain: you have to calculate your current draw and size the wire accordingly. At maximum brightness (full white) the current draw is 60mA per LED. That adds up fast. Just 100 LEDs is already 6A. The thin foil conductors in LED strips are no good for long strips like that — the voltage drop is so severe that a) you get visible color shift towards the end of the chain, and b) the voltage drop reduces current flow in the LEDs, making them visibly dimmer. It’s imperative to feed power in at multiple points throughout the chain. Now, if your application means that only a few LEDs will ever be lit at once, or if you’re running them at lower brightness, you can scale down the current linearly. (Some driver libraries even let you program a current limit.) At maximum brightness, I’d feed in power at least every 100 LEDs, but ideally a lot more, like every 30-50. Note that the length matters too, since voltage drop cares about distance. So I’d also say to feed in power every 3 feet at most.