Combine water and rice in a medium saucepan; bring to a boil. Cover, reduce heat, and simmer 50 to 60 minutes or until rice is tender. Drain well; let cool.
Cut pepper in half lengthwise; remove and discard seeds and membrane. Place pepper, skin side up, on a baking sheet, and flatten with palm of hand. Broil 5 1/2 inches from heat (with electric oven door partially opened) 15 to 20 minutes or until charred. Place in ice water until cool; peel and discard skin. Dice pepper.
Combine rice, red pepper, chopped spinach, and next 4 ingredients in a large bowl; toss lightly.
Combine vinegar and next 5 ingredients in a jar; cover tightly, and shake vigorously. Pour vinegar mixture over rice mixture, and toss well. Cover and chill thoroughly.
To serve, place 3 spinach leaves on each of 4 plates. Top evenly with rice mixture.