4S vs 6S for beginners: stick with 4S. Most beginner-oriented 5-inch quads have 2207 motors wound for 4S, typically 1700-2450KV. 6S motors are different -- typically 1200-1400KV. Running a 4S motor on 6S will destroy it. Running 6S packs on a 4S quad also risks destroying your ESC.
Match the battery voltage to what your quad is designed for. Check the product listing or manufacturer spec sheet -- most quads clearly state 4S or 6S in the title or description. When in doubt, go to the iFlight or BetaFPV product page for your specific model and look for the battery recommendation.