If the outer ring isn't gated (cut teeth) no specific alignment is needed, since shifting will happen anywhere.
OTOH if the outer ring has a shift gate, wrap a length of chain around the ring and lead it over through the gate (as if shifting), and down to the inner ring. Of the 5 possible positions, you want the one where the teeth line up so the chain drops in best (ie. the rollers line up with the troughs between the teeth).
Before Hyperglide, I used to set team cranks up so a chain shifted with the right pedal coming over the top lined up for smooth engagement. Then when riders shifted at the right time they wouldn't get that momentary slippage as the chain looked for engagement.
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