您似乎将start_time()值存储在字符串中。
您可以：

order by appointment_date,
         (case when start_time like '% am' then 1 else 2 end),
         start_time

SQLite并不真正支持日期/时间格式的am/pm，但是使用like可以很容易地实现这一点。

更好的解决方案是将时间以24小时格式存储在多一列中，并且该列的类型应该是DATETIME而不是varchar。
您可以使用以下方法转换时间：

SimpleDateFormat displayFormat = new SimpleDateFormat("HH:mm");
        SimpleDateFormat parseFormat = new SimpleDateFormat("hh:mma");
        Date date=new Date();
        try {
            date = parseFormat.parse(AmPmTimeFormatColumn);
        }catch (Exception e){}
        values.put("24HourFormatColumn", displayFormat.format(date));

然后像这样订购：
从按日期时间（24小时格式列）排序的表名中选择 *;

select
    Date
    , cast(substr(Date, 12, 2) as int) as HOUR
    , substr(Date, 21, 2) as TIME_FORMAT
    , 
        case
            when 
                substr(Date, 21, 2) = 'PM' AND cast(substr(Date, 12, 2) as int) = 12
                then cast(substr(Date, 12, 2) as int)
            when 
                substr(Date, 21, 2) = 'PM'
                then cast(substr(Date, 12, 2) as int) + 12
            when 
                substr(Date, 21, 2) = 'AM' AND cast(substr(Date, 12, 2) as int) = 12
                then 0

            when 
                substr(Date, 21, 2) = 'AM'
                then cast(substr(Date, 12, 2) as int)
        END AS ARMY_HOUR
    , cast(substr(Date, 15, 2) as int) AS MINUTE
from appointment