At least for relatively simple shapes, you may:
1) Create a copy of the character in front, possibly make the original paler and lock it, go on with the copy;
2) Type>Create Outlines and release compound path if relevant;
3) Cut the path so you get two opposite parts, outer/inner or similar, with the same number of Anchor Points (you may add one, or a few, to match);
4) Set Blend options to one step and aligned to path and, create blend, Object>Blend>Expand, and keep only the centre path;
5) Use a colour of your choice and Effect>Stylize>Add Arrowheads.
This should give you a coloured centre path with an arrow over the possible paler character.
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Check the path's fill rule setting and whether it is still designated a compound path or grouzped in some way. Deleting unwanted anchors should be good enough and produce a proper open path.
Thanks Jacob and Myllenium, it now does what I wanted and duplicating angles will be much easier.
For my part you are welcome, Stephen.
Your avatar appears to be a bit broad chested/cheeked. It may be worth considering a square cropping of the original.