It's a French car, and it's old... and the Peugeot 206 tended to have one of the longer lists of potential faults in the used buying guides.
Clutch.... practice to tune yourself into it by doing bite-point checks somewhere out of the way: park up, practice gently moving the clutch up & down until you find the point it starts to move the car.
Hill starts... depends on how much traffic you're having to deal with, but I found it's best to use the handbrake in an unfamiliar car, then work on balancing it on the clutch once you've got more used to it.
You might also want to check any paperwork that came with the car such as receipts for repairs to see when/if it's had the clutch replaced (they can also be a pain in the butt to get used to again going from a knackered clutch to having a fresh one put in with a keener bite point again)..... there's often a cable that can be adjusted to tweak the clutch, but they usually adjust themselves, unless it's a hydraulic clutch like on my similarly aged Ford Fiesta (currently mothballed awaiting repairs due to chassis corrosion).
For further knowledge of the car, you might want to consider getting the Haynes Repair manual for it
For better, more confident driving skills, you may want to consider:
Advanced Driving: How to further skill and enjoyment in motoring by John Lyon (ISBN-10: 085733221X)
Paul Ripley's Expert Driving (ISBN-10: 0716030098)