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Focus coil and ion trap adjustment with the set on is sort of mandatory to do it right. It is possible to be zapped any time a TV is on (and sometimes when it's off) if you are careless. Always work with one hand in your pocket when the set is on (it almost guarantees protection from harmful levels of electric shock).
If the CRT is metal cone don't get your hand closer than 3", beware of yoke and H output tube cap voltages while servicing those can be nastier than HV....I've personally been hit by HV and yoke voltage, and found the yoke triggered my reflexes much more violently.
Voltage rating of a cap is the maximum they will take before blowing up, shorting out etc. It's always fine to select a higher voltage cap. Tolerance rating of a cap applies only to the Capacitance (in farads or micro farads) not voltage.
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